Article No : o02_o11

Ammonia, 2. Production Processes
MAX APPL, Dannstadt-Schauernheim, Germany

1.
2.
3.
4.
4.1.
4.2.
4.3.
5.
5.1.
5.1.1.
5.1.2.
5.1.3.
5.1.4.
5.1.5.
5.2.
5.2.1.
5.2.2.
5.2.3.
6.

Introduction. . . . . . . . . . . . . . . . . . . . . . . .
Historical Development . . . . . . . . . . . . . . .
Thermodynamic Data . . . . . . . . . . . . . . . .
Ammonia Synthesis Reaction. . . . . . . . . . .
General Aspects . . . . . . . . . . . . . . . . . . . . .
Catalyst Surface and Reaction Mechanism
Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . .
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . .
Classical Iron Catalysts . . . . . . . . . . . . . . .
Composition . . . . . . . . . . . . . . . . . . . . . . . .
Particle Size and Shape . . . . . . . . . . . . . . . .
Catalyst-Precursor Manufacture . . . . . . . . . .
Catalyst Reduction . . . . . . . . . . . . . . . . . . .
Catalyst Poisons . . . . . . . . . . . . . . . . . . . . .
Other Catalysts . . . . . . . . . . . . . . . . . . . . .
General Aspects . . . . . . . . . . . . . . . . . . . . .
Metals with Catalytic Potential. . . . . . . . . . .
Commercial Ruthenium Catalysts. . . . . . . . .
Process Steps of Ammonia Production . . .

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1. Introduction
Ammonia is the second largest synthetic chemical product; more than 90 % of world consumption is manufactured from the elements nitrogen
and hydrogen in a catalytic process originally
developed by FRITZ HABER and CARL BOSCH using
a promoted iron catalyst discovered by ALWIN
MITTASCH. Since the early days there has been no
fundamental change in this process. Even today
the synthesis section of practically every ammonia plant has the same basic configuration as the
first plants. A hydrogen – nitrogen mixture reacts over the iron catalyst (today’s formulation
differs little from the original) at elevated temperature in the range of 400 – 500  C (originally
up to 600  C ) and pressures above 100 bar with
recycle of the unconverted part of the synthesis
gas and separation of the ammonia product under
high pressure. End of the 1990s a rutheniumbased catalyst was introduced which allows 
2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.o02_o11

6.1.
6.1.1.
6.1.2.
6.1.3.
6.2.
6.3.
6.3.1.
6.3.2.
6.3.3.
6.3.4.
6.3.5.
6.3.6.
6.3.7.

Synthesis Gas Production . . . . . . . . . . . . .
Feedstock Pretreatment and Raw Gas
Production. . . . . . . . . . . . . . . . . . . . . . . . . .
Carbon Monoxide Shift Conversion . . . . . . .
Gas Purification. . . . . . . . . . . . . . . . . . . . . .
Compression . . . . . . . . . . . . . . . . . . . . . . .
Ammonia Synthesis . . . . . . . . . . . . . . . . . .
Synthesis Loop Configurations . . . . . . . . . . .
Formation of Ammonia in the Converter . . .
Waste-Heat Utilization and Cooling . . . . . . .
Ammonia Recovery from the
Ammonia Synthesis Loop . . . . . . . . . . . . . .
Inert-Gas and Purge-Gas Management . . . . .
Influence of Pressure and other Variables of the
Synthesis Loop . . . . . . . . . . . . . . . . . . . . . .
Example of an Industrial Synthesis Loop . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .

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211
210

slightly lower synthesis pressure and is used in
a few world-size plants (KAAP process of Kellogg – Braun – Root [868–870].
BOSCH was already well aware that the production of a pure hydrogen – nitrogen mixture
is the largest single contributor to the total
production cost of ammonia [18]. So, in contrast
to the synthesis reaction, dramatic changes
happened over the years in the technology of
synthesis-gas generation, and technical ammonia processes differ today mainly with respect to
synthesis-gas preparation and purification. The
elements nitrogen and hydrogen are abundantly
available in the form of air and water, from
which they can be separated by physical methods and/or chemical reactions using almost
exclusively fossil energy. The predominant
fossil fuels are natural gas, liquefied petroleum
gas (LPG), naphtha, and higher petroleum
fractions; coal or coke is used only under special
economic and geographical conditions (China,

140

Ammonia, 2. Production Processes

India, South Africa). Recovery of ammonia
as byproduct of other production processes,
e.g., coke ovens, is no longer of great
importance.
Of course, some of the hydrogen comes also
from the hydrocarbons themselves (methane has
the highest content), and the carbon acts as a
reducing agent for water and in some processes
may also facilitate the separation of oxygen from
nitrogen by formation of carbon dioxide which
can be removed by various operations.

2. Historical Development
The catalytic synthesis of ammonia from its
elements is one of the greatest achievements of
industrial chemistry. This process not only
solved a fundamental problem in securing our
food supply by production of fertilizers but also
opened a new phase of industrial chemistry by
laying the foundations for subsequent highpressure processes like methanol synthesis,
oxo synthesis, Fischer – Tropsch Process, coal
liquefaction, and Reppe reactions. Continuous
ammonia production with high space yields on
large scale combined with the ammonia oxidation process for nitric acid, which was developed immediately after ammonia synthesis,
enabled the chemical industry for the first time
to compete successfully against a cheap natural
bulk product, namely, sodium nitrate imported
from Chile.
The driving force in the search for methods of
nitrogen fixation, of course, was to produce
fertilizers. In principle there are three ways of
breaking the bond of the nitrogen molecule and
fixing the element in a compound:
1. To combine the atmospheric elements nitrogen and oxygen directly to form nitric oxides
2. To combine nitrogen and hydrogen to give
ammonia
3. To use compounds capable of fixing nitrogen
in their structure under certain reaction
conditions.
A vast amount of research in all three directions
led to commercial processes for each of them: the
electric arc process, the cyanamid process, and
ammonia synthesis, which finally displaced the
other two and rendered them obsolete.

Vol. 3

The availability of cheap hydrolelectric power
in Norway and the United States stimulated the
development of the electric arc process. Air was
passed through an electric arc which raised its
temperature to 3000  C, where nitrogen and
oxygen combine to give nitric oxide. In 1904
CHRISTIAN BIRKELAND performed successful
experiments and, together with SAM EYDE, an
industrial process was developed and a commercial plant was built, which by 1908 was already
producing 7000 t of fixed nitrogen. Working
in parallel, SCHOENHERR at BASF developed a
different electric arc furnace in 1905. The Norwegians and BASF combined forces in 1912 to
build a new commercial plant in Norway. However, since at this time pilot-plant operation of
ammonia synthesis was already successful,
BASF withdrew from this joint venture soon
after. Nevertheless, the Norwegian plants operated throughout World War I and had total
production of 28 000 t/a of fixed nitrogen with
a power consumption of 210 000 kW [2]. The
specific energy consumption was tremendous:
60 000 kW per tonne of fixed nitrogen. Had this
electricity been generated from fossil fuels this
figure would correspond to about 600 GJ per
tonne nitrogen, which is about 17 times the
consumption of an advanced steam-reforming
ammonia plant in 1996.
The cyanamide process, [2–5], developed by
FRANK and CARO in 1898, was commercially
established by 1910. Calcium carbide, formed
from coke and lime in a carbide furnace (!
Calcium Carbide), reacts with nitrogen to give
calcium cyanamide, which can be decomposed
with water to yield ammonia. The process was
energetically very inefficient, consuming
190 GJ per tonne of ammonia. Some other
routes via barium cyanide produced from barytes, coke and nitrogen, or using the formation of
titanium nitride were investigated in Ludwigshafen by BOSCH and MITTASCH but did not
appear promising. In 1934, 11 % of world nitrogen production (about 2  106 t/a) [6] was still
based on the cyanamide process, and some
plants even continued to operate after World
War II.
After BERTHOLLET proved in 1784 that ammonia consists of nitrogen and hydrogen and
was also able to establish the approximate ratio
between these elements, many experiments in
the 1800s were aimed at its direct synthesis, but

Vol. 3

remained unsuccessful [7–9]. One of the reasons for the lack of success was the limited
knowledge of thermodynamics and the incomplete understanding of the law of mass action
and chemical equilibrium. It was the new
science of physical chemistry, which developed
rapidly in the late 1800s, that enabled chemists
to investigate ammonia formation more
systematically.
Around 1900 FRITZ HABER began to investigate the ammonia equilibrium [10] at atmospheric pressure and found minimal ammonia concentrations at around 1000  C (0.012 %). Apart from
HABER, OSTWALD and NERNST were also closely
involved in the ammonia synthesis problem, but
a series of mistakes and misunderstandings
occurred during the research. For example, OSTWALD withdrew a patent application for an iron
ammonia synthesis catalyst because of an erroneous experiment, while NERNST concluded that
commercial ammonia synthesis was not feasible
in view of the low conversion he found when he
first measured the equilibrium at 50 – 70 bar
[182, 11].
After a controversy with NERNST, HABER repeated his measurements at atmospheric pressure
and subsequently at higher pressures [12–15],
overcoming his colleague’s preoccupation with
the unfavorable equilibrium concentrations.
HABER concluded that much higher pressures had
to be employed and that, perhaps more importantly, a recycle process was necessary.
The amount of ammonia formed in a single
pass of the synthesis gas over the catalyst is
much too small to be of interest for an economic
production. HABER therefore recycled the
unconverted synthesis gas. After separating the
ammonia by condensation under synthesis pressure and supplementing with fresh synthesis gas
to make-up for the portion converted to ammonia, the gas was recirculated by means of a
circulation compressor to the catalyst-containing reactor. This process, described in the patent
DRP 235 421 (1908), became the basis for the
industrial manufacture of ammonia and since
then the same principle has found widespread
application in numerous high-pressure processes. HABER also anticipated the preheating of the
synthesis gas to reaction temperature (at that
time 600  C ) by heat exchange with the hot
exhaust gas from the reactor, the temperature
of which would be raised by the exothermic

Ammonia, 2. Production Processes

141

ammonia formation reaction sufficiently (about
18  C temperature rise for a 1 % increase of
the ammonia concentration in converted synthesis gas).
In 1908 HABER approached BASF (Badische
Anilin & Soda Fabrik at that time) to seek
support for his work and to discuss the possibilities for the realization of an industrial process.
His successful demonstration in April 1909 of a
small laboratory scale ammonia plant having all
the features described above finally convinced
the BASF representatives, and the company’s
board decided to pursue the technical development of the process with all available resources.
In an unprecedented effort, CARL BOSCH, together with a team of dedicated and highly skilled
co-workers, succeeded in developing a commercial process in less than five years
[16–23]. The first plant started production at
Oppau in September 1913 and had a daily
capacity of 30 t of ammonia. Expansions increased the capacity to about 250 t/d in 1916/17
and a second plant with a capacity of 36 000 t/a
went on stream in 1917 in Leuna. Further stepwise expansions, finally reaching 240 000 t/a,
already decided in 1916, came in full production
only after World War I [3]. After World War I
ammonia plants were built in England, France,
Italy, and many other countries based on a BASF
license or own process developments, with
modified process parameters, but using the same
catalyst.
Up to the end of World War II, plant capacities
were expanded by installing parallel lines of
70 – 120-t/d units, and synthesis-gas generation
continued to be based on coal until the 1950s.
With growing availability of cheap petrochemical feedstocks and novel cost-saving gasification
processes (steam reforming and partial oxidation) a new age dawned in the ammonia industry.
The development started in the USA, where
steam reforming of natural gas was used for
synthesis gas production. This process was originally developed by BASF and greatly improved
by ICI, who extended it to naphtha feedstocks.
Before natural gas became available in large
quantities in Europe, partial oxidation of heavy
oil fractions was used in several plants. The next
revolution in the ammonia industry was the
advent of the single-train steam reforming
ammonia plants, pioneered by M. W. KELLOGG
and others. The design philosophy was to use a

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Ammonia, 2. Production Processes

Vol. 3

single-train for large capacities (no parallel lines)
and to be as far as possible energetically selfsufficient (no energy import) by having a high
degree of energy integration (process steps in
surplus supplying those in deficit). Only through
this innovative plant concept with its drastic
reduction in feedstock consumption and investment costs, could the enormous increase in world
capacity in the following years became possible.
Increasing competition and rising feedstock
prices in the 1970s and 1980s forced industry
and engineering companies to improve the processes further.
The LCA process of ICI (page 97) and the
KRES/KAAP process, which is the first process
since 1913 to use a non-iron synthesis catalyst,
are recent advances that make a radical breakaway from established technology.
A short survey of the history of ammonia
process technology can be found in [20, 21,
24, 25, 331, 834, 841, 874].

3. Thermodynamic Data
Ammonia synthesis proceeds according to the
following reaction:
0:5 N2 þ1:5 H2
NH3 DH 298 ¼ 46:22 kJ=mol

To fix a kilogram of nitrogen in ammonia
requires reacting 2.4 m3 (STP) of hydrogen and
0.8 m3 (STP) of nitrogen. About 3.27 MJ of heat
is evolved. Table 1 is a compilation of the most
important thermodynamic data for the reaction at
atmospheric pressure.
Chemical Equilibrium. The reaction equilibrium has been investigated experimentally and

theoretically many times. Values for the equilibrium constant are available for pressures up to
350 MPa (3500 bar).
GILLESPIE and BEATTIE [26] (see also [1]) were
by far the most successful experimentally in
establishing a firm basis for an analytical expression of the equilibrium constant in the range of
industrial interest. The values in Tables 2 and 3
were calculated using their equation. A detailed
description, with literature data and many tables,
appears in [1]. A description of the equilibrium
using the REDLICH – KWONG equation of state is
given in [325].
Heat of Reaction. HABER investigated the
heat of reaction at atmospheric pressure [27].
Numerous authors have estimated the pressure
dependence under various assumptions. Today,
most people use the Gillespie – Beattie equation
[28]. This equation was used in calculating the
values in Table 4. For further data see, for example, [1]. Reference [29] contains test results for
the range 120 – 200 MPa (1200 – 2000 bar)
and 450 – 525  C. Additional literature can be
found in [30]
Physical Properties of the Reactants. Various authors have measured the p – V – T behavior of nitrogen, hydrogen, and 3 : 1
hydrogen – nitrogen mixtures. Reference [1]
contains a survey. For the specific heat, thermal
conductivity, and viscosity of the reactants,
see [31, 32]. It is to be noted that heats of
mixing must be considered for synthesis gas.
This applies especially for high pressures and
low temperatures. Reference [33] gives viscosities of hydrogen – nitrogen and hydrogen –
ammonia mixtures.

Table 1. Thermodynamic data for the reaction 0.5 N2þ1.5 H2
NH3 at atmospheric pressure
t, K

DH, kJ
DS, J K1
DG/T, J K1
cp, NH3, J mol1 K1
cp, H2, J mol1 K1
cp, N2, J mol1 K1

300

400

500

600

700

800

900

1000 

46.35 
99.35 
55.22
35.52
28.868
29.144 

48.48 
105.63 
15.66
38.80
29.199
29.270 

50.58 
110.03
8.88
41.97
29.278
29.601 

52.04 
112.71
26.25
45.04
29.341
30.132 

53.26 
114.55
38.48
47.98
29.454
30.777 

54.28 
115.89
48.02
50.80
29.634
31.451 

55.06 
116.77
55.56
53.49
29.89
32.117 

55.68 
117.48
61.81
56.03
30.216
32.724

50 40.39 44.68 35.57 92.16 19.51 43.73 82.94 37.47 49.67 41.52 84.99 61.23 14.23 13.02 16.43 68.64 25.94 87.42 72. N2 :H2¼1 : 3 t.96 47.59 4.94 39.53 43.75 45.32 49.59 86.61 55.25 52.03 89.74 19.00 4.39 59. MPa 5 10 20 30 40 50 60 70 80 90 100 39.80 70.41 62.67 16.68 12.10 18.38 39.52 87.04 70.35 75. the theoretically achievable ammonia yield is extremely small because of the unfavorable position of the thermodynamic equilibrium.60 29.58 43.20 5.42 91.68 27.85 30.46 75.57 12.52 83.97 44.74 84.Vol.46 6.69 20.20 27. significant energy input is required for the nitrogen molecule to achieve the activated state.33 27.24 15.80 53.41 11. 2.41 39.46 44.36 10.58 70.71 27.76 88. this activation barrier requires temperatures well above 800 – 1200 K to achieve measurable reaction rates.75 25.00 7.53 77.33 65.71 33.43 77.26 42.96 58.81 63.48 35. the formation of ammonia may be forced by employing other forms of energy. On the other hand.75 69.21 33.55 27.69 79.39 92.64 63.20 66.61 17.38 17.20 71.36 46.49 20.33 46.99 67.85 62.81 40.87 35.02 34.02 32.39 67.34 6.49 3.89 35.12 5.19 65.79 57.17 41. a system having an exothermic heat of reaction under operating conditions should react spontaneously. initiation of ammonia synthesis homogeneously in the gas phase requires an activation energy of 230 – 420 kJ/ mol.95 57.95 32.22 90.34 80.26 37.12 85.52 79.97 81. For purely thermal energy supply with a favorable collision yield.53 68. 186]).65 33.72 68.95 83.47 41. At pressures above 200 MPa (2000 bar).98 86.09 82.97 63.49 77.15 84. At such extreme pressures the vessel walls appear to catalyze the formation of ammonia.15 23.46 44. In the homogeneous phase under thermodynamically favorable temperature conditions.46 28.08 64.89 63. such as electrical energy or ionizing radiation.31 58.79 37.22 65.1.96 41.21 29.29 59.20 55.98 81.59 13.29 85.26 30.65 31.12 22. This is because of its high dissociation energy of 941 kJ/mol.95 21. General Aspects Usually.38 81.14 75. The principal difficulty with these so-called plasma processes.28 52.67 76.43 69.24 7.84 22.42 69.79 49.66 77.79 41.35 87.40 60.35 22.26 29.22 42. 3 Ammonia.33 58.69 74.41 60.72 87.13 46.63 62.74 6.10 9.72 40.65 14.48 66.16 37. both ammonia and hydrazine result from reacting atomic nitrogen with atomic hydrogen (see for example [34.08 21.19 48.12 8.85 60. to form ammonia from hydrogen and nitrogen molecules.29 73.18 77.  C 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540 550 560 570 580 590 600 pabs.06 48.64 16.88 10.74 10.62 48.92 34.84 39.84 32.37 50.93 64.05 4.61 89.36 31.09 56.91 47.50 20.22 23.02 82.87 37.69 61.63 60.20 49.79 20.80 53.81 46.78 54.79 70.57 33.93 2.13 24.72 8.43 46.04 52.85 4.66 55.57 73.70 5.48 37.90 24.38 36.28 67.05 39.37 84. Ammonia Synthesis Reaction 4.53 71. Ammonia content (in mol %) in equilibrium synthesis gas.13 43.39 21.50 56.54 78.92 50.39 9.67 11.96 14.52 74.34 18.64 18.41 37.33 80.14 91.49 78.92 55.06 52.82 3.04 32.05 53.37 29.87 15.26 4.23 66.80 15.61 82.69 2.59 71.26 27.88 21.34 25.40 11. In fact.72 75.13 18.06 28.86 42. According to estimates [34].62 33.92 42.60 60.75 6.23 69.71 74.25 79.04 33.43 63.26 57.53 36.36 62. Production Processes 143 Table 2.35 90. However.86 45.60 58.71 31.20 2.60 55.12 72.74 12.80 35.89 35.99 60.51 79.19 50.84 17.74 46.39 55.24 20.48 52.19 3.69 65.19 10.69 73.68 72.20 86.97 31. all older attempts to combine molecular nitrogen purely thermally with atomic or molecular hydrogen failed.19 30.06 55.49 22.80 27. .17 49.37 26.55 51. the synthesis of ammonia proceeds even in the absence of specific catalysts.20 88.88 48. at such high temperatures and industrially reasonable pressures.63 46.54 75.45 40.56 5.88 34.54 23.74 16.21 23.81 38.83 93.01 72.42 51.36 25.93 65.52 8.60 12.89 53. which is considerably higher than that of hydrogen.36 8.13 79.03 43.28 81.50 47.12 38.84 13.83 88.15 25.09 9.54 25.62 84.20 30.60 34.16 37.87 53. p.77 13.55 76.61 31.86 26.47 2.61 51. However.91 58.77 37.07 29.

References [36–39] give reviews of the older and some of the newer literature.65 37. Iron catalysts which are generally used until today in commercial production units are composed in unreduced form of iron oxides (mainly magnetite) and a few percent of Al.46 23.12 75.77 36.65 54.27 3.81 76.01 23.31 20.56 69.48 41.84 49.49 39.19 16.56 70.57 55.02 29.81 14.49 25.17 20.21 7.29 61.72 43. Ca.64 4.25 43.50 18.62 58.90 45.01 34.10 2.73 12.04 4.78 32.66 31.17 37.22 67.24 8.20 34. it was discovered that electron donor – acceptor (EDA) complexes permit making ammonia with measurable reaction rate at room temperature.27 62. 2.96 18.09 11.38 56.49 57.79 14.80 15.91 40.08 63.51 37.36 69. The reaction may then proceed in the temperature range 250 – 400  C.37 49.09 6.94 38.81 59.06 5.22 12.93 68.44 13.81 47.05 18.31 70.71 22.86 47.68 72.17 33. the molecules lose their translational degrees of freedom by fixation on the catalyst surface.31 75.87 43.28 27.93 32.67 23.97 4.86 45.26 47.69 19.04 29.33 22.64 55.40 47.51 53. Production Processes Vol. to 103 kJ/mol on iron [35].96 30.42 26.68 61.79 64.83 39. is that the energy supplied is useful only in part for ammonia formation.18 2. Prereduced catalysts are also commercially available.81 21.97 49. This section concentrates mainly on the ammonia synthesis reaction over iron catalysts and refers only briefly to reactions with non-iron catalysts.74 7.33 9.89 19.39 11.09 27.35 74.14 58.78 53.10 3. Equilibrium ammonia content (in mol %) in the presence of inert gases (2.12 10.05 24.23 19.92 22.95 63.07 13.51 44.36 41.33 28.48 29.07 34.87 24.90 32.03 72.63 7.02 42.63 56.96 52.54 31.12 24.60 16.98 22.97 38.73 13.02 12.87 31.29 25.11 9.51 25.59 64.31 38.85 53.93 26.68 43.13 37.63 16.5 mol % CH4).66 47. Since the 1980s a large variety of surface science techniques involving Auger electron spectroscopy.11 50.64 27.52 59.56 16.67 41.46 18.94 3.39 20.18 62.49 71. scanning tunnelling microscopy.41 15.27 24.36 20.97 39.44 25.86 51.40 3.37 73.01 32.26 34.38 46.19 13.68 28.69 63. Numerous investigations have been performed to elucidate the mechanism of catalytic reaction of nitrogen and hydrogen to form ammonia.50 18.77 33.58 47.77 33.144 Ammonia. In 1972.44 51.41 35.43 which also impedes their economic use.85 49.95 20.10 8.89 29.30 50.72 12.96 15. Xray photoelectron spectroscopy.96 35.98 63.01 1.80 29.77 66.08 30.69 43.83 38.65 71.79 55.64 42.11 47. 3 Table 3.92 30. MPa 5 10 20 30 40 50 60 70 80 90 100 32.92 39.46 33. Activation is usually accomplished in situ by reduction with synthesis gas.59 2.79 66.37 32.06 51.75 41. 7.49 61.50 72.28 64.19 14.79 11.68 34.24 65.70 67.76 64.54 70.09 58.87 8.37 64.16 45.39 68.24 15.09 29.39 56.89 63.38 2.28 74.51 20.25 48.28 21.56 45.87 70.34 32.62 23.10 40.49 4.84 60.87 53.75 34.48 15.14 45.73 52. Many of these methods are based on .16 69.86 50.48 57.83 2.27 51.50 5.02 25.03 59.85 43.75 60.57 54.03 30.48 27.52 55.56 23.57 21.03 57.38 72.41 6. 43].59 19. N2 :H2¼1 : 3 t. other elements such as Mg and Si may also be present in small amounts.65 37.85 22.52 60.34 53.74 53.16 10.31 71.81 51.51 4.62 40.45 13.05 11.24 27.81 17.44 27.99 71.02 61.29 59. and others have been developed [42.98 49.08 60.79 40.64 54.76 17.73 3.30 38. This drastically reduces the required energy of activation.76 45.48 5.63 67.24 49.36 64.52 49.97 5.88 41.49 32. temperature-programmed adsorption and desorption.65 22.68 57.04 68.51 74.30 22.57 54.08 36.76 31.20 61.5 mol % Ar.51 25. work-function measurements.21 55.97 29.52 68.65 26.11 29.47 27.22 7.32 57. A greater part is transformed in primary collision and exothermic secondary processes into undesirable heat or unusable incidental radiation.79 17.43 14.01 35.32 44.09 40.06 47.84 36.38 59.46 7.38 30.23 27. In the catalytic combination of nitrogen and hydrogen.64 39.18 10.70 6.10 67.63 73.61 30.03 66.63 45.59 31.10 17.12 66.35 61.96 42.92 11.68 35. for example.84 35.45 52.57 8.71 16. and K.96 26.90 42.08 9.05 10.  C 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540 550 560 570 580 590 600 pabs.59 65.52 27.06 36.46 51.56 36.71 43.29 39.67 69.27 65.

17 51.55 67.31 54.98 55.26 87.72 63.92 53.12 59.10 55.86 61.29 58.00 79.28 54.  C 0 25 50 75 100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 pabs.42 57.56 130.40 59.10 64.22 60.40 52.12 57.14 63.55 58.03 59.84 70.41 56.76 84.3).23 57.64 62.48 89. The transport processes occurring in the pores of the catalyst in accordance with the classical laws of diffusion are of importance in industrial synthesis (see also Sections 5.69 51.55 61.83 65.44 58.48 57.55 52.34 51.75 60. if need be with participation by hydrogen from the gas phase.28 62.27 67.86 54.47 87.02 62.18 61.47 46.09 54.2 and 4.35 53.47 58.18 55.03 80.62 61.5 N2þ1.19 71. 82.50 58.02 52.86 60.39 44.83 70. 2. from [26] t.14 60.43 120.82 93. 3 Ammonia.01 69.46 59.37 51.20 53.71 53. Adsorption of the reactants (and catalyst poisons) on the inner surface 3.61 98.20 57.60 60.60 56.58 62.86 63.43 58.68 56.38 100.89 72.78 83.66 79.88 64.33 49.63 62.00 62.30 57.48 58.05 75.71 58.Vol.64 54. 4.20 57.52 59. Desorption of the ammonia formed into the gas phase 5.57 59. or neutral particles and exhibit high sensitivity to surface structures.16 75.80 97. 69–75.28 53.39 59.17 53.86 64.92 56.49 114.51 65.81 57.06 58.88 68.97 47.28 51.52 54. to form activated intermediate compounds 4. MPa 0 (ideal) 10 20 30 40 50 60 70 80 90 100 44.46 54.04 83.28 61.76 59.62 68.37 64.60 63.26 55.06 61.48 64.33 61.15 152.44 68.69 55.50 62.48 52.11 104.38 56.69 61.04 60.59 66.29 57.01 53.44 61.84 61.82 53.70 55.42 48.00 55.59 88.28 52.34 69. Transport of the ammonia through the pore system and the laminar boundary layer into the bulk gas stream Only the portion of the sequence that occurs on the catalyst surface is significant for the intrinsic catalytic reaction.85 63. Catalyst Surface and Reaction Mechanism Earlier studies [67.77 52.83 75. and further through the pore system to the inner surface (pore walls) 2.78 66.67 55.61 53.92 113. Transport of the reactants by diffusion and convection out of the bulk gas stream. the course of ammonia synthesis by the Haber – Bosch process can be divided into the following steps: 1.52 109.76 50.09 64.18 57.82 55.88 91.04 62.86 53.74 55.48 69.88 66.78 62.91 59.36 51.58 61.90 64.46 47.06 51.54 57.95 65.66 58.39 60.73 52.03 56.19 57.02 51.76 53.72 60.37 57.44 75.76 53.55 57.14 63.53 66.70 87.47 71.24 141.73 103.66 55.54 51.97 55.74 121.40 61.23 63. This has now been fully confirmed by microkinetic . Heat of reaction DH (in kJ) for the reaction 0.79 76. This assumption is decisive in representing the synthesis reaction kinetics. 44].58 70.74 65.05 65.82 58.95 86.02 80.84 63.96 61.96 46.87 66.93 107.14 56.80 55.82 59. Of special importance is the adsorption of nitrogen.26 56.08 51.57 54.41 63.38 59.68 60.71 54.44 45. and it was also possible to identify adsorbed intermediates.1.80 53.59 67.52 60.28 56.94 73.32 62.92 45.44 59.43 58.06 62.98 54. The results of these experiments allow the mechanism of ammonia synthesis in the pressure range of industrial interest to be elucidated [40.99 51. Production Processes 145 Table 4.72 67.2. Reaction of the adsorbed species.65 59.53 63.26 57.50 56.19 54.70 80.94 73.95 48.49 64.06 interaction of slow electrons.86 65.59 50.09 53.53 53.42 62.45 61.61 64.91 59.5 H2 NH3.45 58.29 96. to the outer surface of the catalyst particles. ions.23 63.45 60.34 71.79 53. With these powerful tools the kinetics of nitrogen and hydrogen adsorption and desorption could be investigated.82 55.66 65.00 63.62 63.94 79.51 55.88 49.53 67.23 63.72 72.20 94. 41. 197] had already suggested that on iron catalysts nitrogen adsorption and dissociation can be regarded as the ratedetermining step for the intrinsic reaction.18 50.16 68.31 75.69 66.17 60.97 79.93 63.39 60.35 55.27 63. through a laminar boundary layer.07 52. As with every catalytic gas-phase reaction.35 57.09 74.48 59.15 73.34 130.12 54.43 58.

From experimental results it was concluded that for hydrogen a direct transition from the gaseous H2 molecule into the chemisorbed Had is most likely. Isotopic experiments with 30N2 and 29N2 showed that the surface species resulting from lowtemperature adsorption was molecular. Measurements on defined single crystal surfaces of pure iron performed under ultrahigh vacuum [78–80] clearly showed that Fe(111) is the most active surface. 2. Ammonia synthesis is highly sensitive to the orientation of the different crystal planes of iron in the catalyst [99–103]. it increases as the surface becomes increasingly covered with adsorbed nitrogen species. In IR spectroscopic investigations. 76] . In the case of nitrogen the first step seems to be an adsorption in molecular state followed by chemisorption in the atomic state. Activation energy. but subsequently dissociates when the temperature is raised. This was also demonstrated by the rate of ammonia formation on five different crystallographic planes for unpromoted iron at 20 bar. NH and NH2 species were identified [77]. Under reaction conditions it can attain values of 63 – 84 kJ/mol [44. Ammonia formation rate on different iron surfaces [48. 76]. adhesion coefficient (the probability that a nitrogen molecule striking the surface will be adsorbed dissociatively) and work function show a clear dependence on surface orientation [48. It was further shown that at lower temperatures nitrogen becomes adsorbed only in the molecular state. reactivity. 3 simulations based on the results of surface science studies [40. whereas that from high-temperature adsorption was atomic [107]. 70] which are typical for ammonia synthesis. 69.146 Ammonia. Production Processes Vol. as shown in Figure 1. 54. and secondary ion emissions detecting NHþ also confirmed the presence of NH species on the surface [105]. 66. In single-crystal experiments it was found that the activation energy for dissociative nitrogen adsorption is not constant. 98]: Ammonia synthesis activity: (111) > (211) > (100) > (210) > (110) Activation energy of nitrogen adsorption: (111) > (100) > (110) Work function: (210) > (111) > (211) > (100) > (110) Surface roughness: (210) > (111) > (211) > (100) > (110) Figure 1. and evidence for the stepwise hydrogenation of surface nitrogen atomic species was found.

A similar effect was not found for the ammonia synthesis at 20 bar and catalyst temperature of 400  C: only a two-fold increase of the ammonia formation rate was measured for Fe(111) and Fe(100). Other experiments [83] show that even the least active face Fe(110) becomes as active for the synthesis as Fe(111) after addition of alumina with subsequent annealing with oxygen and water vapor. temperature programmed desorption and electron microscopy – assumes that first alumina forms an iron aluminate FeAl2O4 on the surface. This argument might probably be the key for the special role of C7 sites. 2. about 100 kJ/mol [67. A proposed mechanism for these findings – backed by X-ray photoelectron spectroscopy. respectively) to the effect that the differences in surface orientation disappear [839].ad þHad NH3. 68].Vol. A possible explanation for the high activity of faces (111) and (211) is that these are the only surfaces which expose C7 sites (iron with seven nearest neighbors) to the reactant gases.ad ð5Þ NH2. 95–97]. 88]. 96] adsorption on the planes Fe(111) and Fe(110) is associated with a regrouping of the surface atoms. 700 K) used in industrial ammonia synthesis. Promotion with potassium of single iron crystals enhances the sticking probability for nitrogen dissociation much more on the Fe(100) and (110) than on the Fe(111) (factors 280.ad ð6Þ NH3. The subsequent hydrogenation steps are energetically uphill. Adsorption and desorption under higher pressure on finely dispersed catalyst indicate that the reaction is highly activated under these conditions with high coverage. but the energy differences involved can easily be overcome at the temperatures (ca. Industrial ammonia synthesis in the homogeneous gas phase is not feasible because of the high dissociation energies for the initial steps. These values increase significantly for higher coverage [96. This new surface then may serve as a template on which iron grows with (111) and (211) orientation upon exposure to the synthesis-gas mixture in the reaction [84]. There are theoretical arguments [85] that highly coordinated surface atoms should show increased catalytic activity due to low-energy charge fluctuations in the d-bands of these highly coordinated atoms. Other reasons discussed are based on charge transfer and interaction of iron d-bands with antibonding 2 p* orbitals of nitrogen [81]. 3 Ultrahigh vacuum (UHV) experiments with single crystals show that the activation energy of the nitrogen adsorption at zero coverage increases from about zero for Fe(111) to 21 kJ/mol for Fe(110) [40. The reaction over a catalyst avoids this problem since the energy gain associated with the surface atom bonds overcompensates these dissociation energies and the first steps have actually become exothermic. not so much on account of its activation barrier but rather because of the very unfavorable preexponential factor in its rate constant. Some critics [86] of the above energy diagram question the low net activation barrier from the gas phase. According to [95.ad NH3 þ ð7Þ The progress of the reaction may be described in the form of an energy profile. The arguments are based on an analysis of activation energies from early measurements of the nitrogen adsorption kinetics on singly (Al2O3) promoted catalysts and on the results of experiments with supersonic molecular beams [87. as shown in Figure 2. Production Processes 147 Based on these experimental results a reaction scheme for the ammonia synthesis may be formulated comprising the following sequence of individual steps [40]: H2 þ  2 Had ð1Þ N2 þ  N2. . Dissociative nitrogen adsorption remains nevertheless the rate-determinating step. Ammonia.ad ð2Þ N2. It is. quite apparent that the rate-controlling step would switch from dissociative nitrogen adsorption to hydrogenation of adsorbed atomic nitrogen species if the temperature were lowered sufficiently because of these differences in activation energy.ad 2 Nad ð3Þ Nad þHad NHad ð4Þ NHad þHad NH2. ca. 97]. and the face (110) was found to be inactive with and without potassium [48]. however. 1000 and 8. 69.

A critical evaluation of the present knowledge of the mechanism of the synthesis reaction was € [97]. With still (111) faces present in the reduced state the catalyst has a higher specific surface area and an improved pore structure. 102. KM IR. the question whether the active industrial catalyst exposes mostly (111) faces remains unresolved. Thus the following picture for the nitrogen adsorption emerges: N2 !S  N2 ðg stateÞ!S  N2 S  ða stateÞ !2 S  Nðb stateÞ where S* denotes a surface atom. whereas the g state is regarded as a terminally bound species. For industrial catalysts made by careful reduction of magnetite fused with nonreducible oxide promoters the important role of the (111) face seems to be confirmed [47]. . further improvements of the catalyst are at least theoretically possible [90]. NIELSEN et al. or of adsorption complexes containing diatomic nitrogen. Schematic energy profile of the progress of ammonia synthesis on Fe (energies in kJ/mol) [40] An attempt to explain these differences is given in [89]. They found evidence that a different reaction mechanism predominates below and above 330  C [116]. This was indeed the case with the new AmoMax-10 catalyst [844. If not. Production Processes Vol. In more recent investigations of the adsorbed nitrogen species [91–94] a second molecularly adsorbed species was detected. investigated ammonia synthesis on a commercial Topsøe catalyst. at low temperatures.15. in the rate-determining step (see [36. However. chemisorbed hydrogen blocks the catalyst surface [117].148 Ammonia. 37] for further literature).03 to 0. This catalyst in its oxidic form is based on wustite instead of magnetite and has a significantly better activity at lower temperature than magnetite. These propose participation of diatomic nitrogen. 845] of S€ udchemie. Wustite is a nonstoichiometric iron oxide(Fe1xO) with a cubic crystal structure. Also. over a wide temperature range. This so-called a state was interpreted as a bridgebonded species with electron donation from the surface to the antibonding p levels of N2. The latter finding is in agreement with the observations of ERTL’s group [66]. 104–115]. 3 Figure 2. made by SCHLOGL Other reaction mechanisms have been debated for reaction temperatures below 330  C [51. 2. x ranging from 0.

4).Vol. Tc. High temperatures accelerate ammonia formation but imply a lower value of the equilibrium ammonia concentration and so a lower Figure 4. Ni. Mo. 127]. molybdenum [123–125]. Reaction rate for NH3 synthesis. This is somewhat surprising in view of the marked differences in the heats of adsorption of nitrogen and the adsorption activation energy. Co. Kinetics Knowledge of the reaction kinetics is important for designing industrial ammonia synthesis reactors. Production Processes 149 Reaction Mechanism on Non-Iron Catalysts.3. Rh and their alloys (no nitride formation under synthesis conditions) Mn. This means predicting the technical dependence on operating variables of the rate of formation of ammonia in an integral catalyst volume element of a converter. Figure 3. which has no significant activation energy and a high adsorption enthalpy for nitrogen. 2. for determining the optimal operating conditions. and for computer control of ammonia plants. uranium [119]. Non-iron systems which exhibit some potential to catalyze ammonia synthesis can be divided into the following groups [120]: . Therefore. This even holds for tungsten. Platinum group metals such as Ru. Specific references: vanadium [118]. 120–122. 3). Dependence on the ammonia concentration at various pressures driving force. V (present as nitrides under the reaction conditions) In the non-iron systems the rate-determining step is also dissociative adsorption of nitrogen and the catalyst effectivity seems to be primarily dictated by the activation energy of the dissociation reaction [120]. . activity and reaction mechanism of non-iron catalysts is given in [37. the rate of formation at first increases with rising temperature but then goes through a maximum as the system approaches thermodynamic equilibrium (Fig.3). Pt (no nitrides) Mn. high ammonia concentration in the synthesis gas (recycle gas) restricts it (Fig. . The factor common with the iron catalyst is the structure sensitivity. tungsten [126]. Further information on structure.2. The only system which seems to be promising for industrial application is ruthenium promoted with rubidium on graphite as carrier (see Section 5. so that hydrogenation of adsorbed atomic nitrogen could be expected to be the rate-determining step. Reaction rate for NH3 synthesis. Os Ir. High pressure promotes a high rate of ammonia formation. 3 Ammonia. 4. Dependence on the temperature at various pressures .

Figure 5. Classical Expressions for Ammonia Synthesis Kinetics.1. Equations for describing ammonia synthesis under industrial operating conditions must represent the influence of the temperature. are described by theoretically deduced formulas. The first expression useful for engineering purposes was the Temkin – Pyzhev Equation (1) proposed in 1940 [129. that hydrogen and ammonia have no significant influence on nitrogen adsorption. insofar as they have been based on measurements in the operating range of commercial interest. in accordance with an equilibrium depending on the temperature and the water vapor – hydrogen partial pressure ratio. which are significant in industrial ammonia synthesis. This may be attributed to a hindering effect of adsorbed hydrogen at low temperature [117]. Figure 5 presents data obtained using a commercial iron catalyst. a high ratio of bed length to bed diameter is chosen. In some investigations. Experimental measurements. emanating in each case from a proposed reaction mechanism Experimental Measurements of Reaction Kinetics. 130]. Sometimes the catalyst is also diluted with inert material. Topsøe KMIR.150 Ammonia. the gas composition. 3 or from empirical evaluations.5 – 1. especially in the earlier literature. reversible poisoning of the adsorbing areas. A discussion of kinetics proposed up to 1970. free of mass-transfer restrictions. must be taken into account when developing rate equations (see also Section 5. 52–54]. usually made with very fine particles. It is based on the assumption that dissociative adsorption is the rate-determining step. Moreover. To exclude any poisoning by the synthesis gas. If oxygen compounds are present in the synthesis gas. very pure reactants were prepared by decomposition of anhydrous ammonia [52].4). the validity of which is tested experimentally by their possibility for extrapolation to other reaction conditions. The reaction expressions discussed in the following model the intrinsic reaction on the catalyst surface.5 mm to avoid pore diffusion restriction and heat-transfer resistance in the catalyst particles. differential reactors were used. An evaluation of present knowledge is given in [40. Since the beginning of commercial ammonia synthesis. and the equilibrium composition. To exclude maldistribution effects and back mixing. The data show a sharp drop in reaction rate with declining temperature at H2 / N2 ¼ 3 : 1 ratio in contrast to a H2 /N2 ¼ 1 : 1 ratio. Contradictory data on the kinetics of ammonia synthesis. Production Processes Vol. Ammonia synthesis rate constant dependence on hydrogen – nitrogen ratio A similar situation exists for the dependence of the reaction rate on the ratio of the hydrogen and nitrogen partial pressures. the pressure. and that the kinetics of nitrogen adsorption and desorption can be described adequately by Elovich-type adsorption . 5). A critical review of the data and equations published up to 1959 appears in [128]. the maximum rate shifts to a lower hydrogen – nitrogen ratio (Fig. can be found in [51]. 2. Commonly the isothermal integral reactor is used with catalyst crushed to a size of 0. in some circumstances may reflect a lack of attention to the influence of impurities in the gas. they must also take into consideration the dependence of the ammonia formation rate on the concentration of catalyst poisons and the influence of mass-transfer resistances. a large number of different kinetic equations have been suggested. with lower temperature.

used by NIELSEN et al. [151.5 [132–134] and 0. acquired with all the modern spectroscopic techniques. 4). An important modification was made by TEMKIN [131] who incorporated hydrogen addition to the adsorbed nitrogen as a second ratedetermining step (Eq. 136] were used. The data from single-crystal experiments for potassium-promoted Fe(111) surface were used for the rate of the dissociative nitrogen adsorption. is a combination of these model equations. Values for the factors a between 0. 51]. 2) was often used [137.75 [1. to attempt the generation of a kinetic expression for ammonia synthesis from a . Potential energy diagrams for the various intermediate steps and species. 152] and STOLTZE and NøRSKOW [153. A similar equation is found in [142]. developed by OZAKI et al. The best results have been achieved so far by calculating the overall rate from the rate of dissociation of the adsorbed nitrogen and equilibrium constants for all other reaction steps. ICI demonstrated that this equation gives a better fit with experimental data [143]. The applicability of a particular equation resulting from this concept also depends on the state of reduction of the catalyst [139. Equation (3) transforms into Equation (1) [116. It was also shown later that the original Equation (1) is a simplified form of a more general model which can be derived from the concept of energetically homogeneous (Langmuir – Hinshelwood adsorption isotherm) as well as for heterogeneous surfaces (Elovich-type isotherm). Production Processes 151 on an energetically inhomogeneous surface. thermodynamical equilibrium. a simpler expression (Eq. were set up and Arrhenius expressions for each single step with known or estimated values for all pre-factors and activation energies were formulated. where the converter feed has always a certain ammonia content) was the fact that for zero ammonia content. The adsorption – desorption equilibria were treated with approximation of competitive Langmuir-type adsorption and by evaluation of the partition functions for the gaseous and adsorbed species. 41. 2. Equation (3). that uses fugacities instead of partial pressures. 140] and the type of promoter [141]. Comparison of the calculated ammonia yields with those determined experimentally on a commercial Topsøe KM1 catalyst showed an agreement within a factor Surface Science Based Ammonia Kinetics [40. 3 Ammonia. and the rate constants on pressure [116. Near the detailed microscopic model of the reaction mechanism consisting of a number of discrete steps at molecular and atomic level. [144]. Additionally. the equation gives an infinitely high reaction rate. 135–139].Vol. 135. as in some laboratory measurements. 138]. 154]. such as BOWKER et al. 53] are presently still viewed as an academic exercise rather than as a practical tool for engineering. To avoid this. has prompted some research groups. For many years this kinetic expression was the basic design equation for ammonia converters. a number of modified equations were proposed and tested with existing experimental data and industrial plant results [146–149]. More serious (not so much for industrial purposes. [145]. A problem with this equation was that the a values (reaction order) were dependent on temperature. 52. The large amount of available data on nitrogen and hydrogen adsorption from ultrahigh-vacuum studies on clean iron surfaces.

For this reason the largest concentration gradient (with respect to the concentration in the bulk gas stream) is within the catalyst particles. Since the thermal conductivity of the iron catalysts is much higher than that of the synthesis gas. The high velocity of the gas passing through the converter creates sufficient turbulence to keep the film thickness rather small in relation to the catalyst grain size. For practical application.045 7. These conclusions have been confirmed by calculations results of another independent group [54. the apparent energy of activation falls to about Table 5. It also appears that the effects are oppositely directed and will partly compensate each other. 156].5 mm). vol% from inlet NH3 concentration in bulk gas.5 483. To compete with the empirical models (Temkin and improved expressions) for the best fit to experimental data cannot be the prime objective of the microkinetic approaches. Production Processes Vol. Comparison of ammonia concentrations calculated from surface science kinetics with experimentally measured values [154.0 428. Transport Phenomena. the major temperature difference is in the external gas film. mol% Temperature in bulk gas. 3 Figure 6.000 9. intra particle transport of the reactants and ammonia to and from the active inner catalyst surface may be slower than the intrinsic reaction rate and therefore cannot be neglected.  C 0 20 40 60 80 100 2. For pore diffusion resistances in reactions having moderate heat evolution.9 505. they are means of checking whether our knowledge and understanding of the elementary steps correspond to the reality of catalysts under industrial synthesis conditions.300 10. 2.1 481.536 400. 155] better than 2. For the particle sizes used in industrial reactors (1.4 429.1 455. Rather.5 522.3 .5 456.  C Temperature at catalyst surface. The overall reaction can in this way be considerably limited by ammonia diffusion through the pores within the catalysts [150]. while the catalyst particles themselves operate under approximately isothermal conditions.500 5.152 Ammonia. the following phenomena characteristically hold true in industrial ammonia synthesis [157]: in the temperature range in which transport limitation is operative. Mass and heat transfer effects at the external surface of catalyst particle Position in catalyst bed. This is often used as a correction factor for the rate equation constants in the engineering design of ammonia converters.6 523. mol% NH3 concentration at catalyst surface.592 4.7 401. So it can be concluded that their combined influence on the reaction rate is negligible compared to inaccuracies of the experimental data for the intrinsic catalyst activity [52].778 9. One aspect is interparticle mass transfer and heat transfer through the stagnant film which surrounds the catalyst particles. Figure 6 demonstrates these encouraging results.500 2.2 506. The ratio of the actual reaction rate to the intrinsic reaction rate (absence of mass transport restriction) has been termed as pore effectiveness factor E.960 7. the above kinetic equations have to be modified to make allowance for mass and energy transfer since the reaction rates actually observed in a commercial converter are lower.361 10. As can be seen from Table 5 the differences in temperature and ammonia concentration between the bulk gas stream and the external catalyst surface are small.288 6.500 4.

For a given operating pressure and desired production. Although the proportionate cost of catalysts compared to the total cost of a modern ammonia synthesis plant is negligible. Catalysts The ammonia synthesis catalyst may be viewed as the heart of an ammonia plant. as well as the ammonia production per unit volume of catalyst.equilibrium cNH3 Þ ð8Þ For this case.5 R) (2) and pore effectiveness factor. 12 % inerts. The highest possible insensitivity to oxygenand chlorine-containing catalyst poisons. Production Processes Figure 7.7-mm particles is only about a quarter of the rate measured on very much smaller grains (Fig. the effective rate of formation of ammonia on 5. 163–165]. and so the operating pressure. 5. Industrial catalysts for ammonia synthesis must satisfy the following requirements: 1. E (3) 21. decrease with increasing catalyst particle size [150][158–160]. particle diameter. It also indirectly influences the make-up gas purity requirement. which on account of the complex kinetics of ammonia synthesis cannot be solved analytically. 2. which may be present in even the very effectively purified synthesis gas of a modern . With catalysts that would function at a reaction temperature about 100 K lower. which corresponds to a 535  C equilibrium temperature. 163. or the pressure may be reduced to 15 MPa (compare Tables 1 and 2). Exact numerical integration procedures.Vol.7 mm half its value at low temperatures. Average commercial catalysts yield about 25 vol % ammonia when operating at 40 MPa (400 bar) and 480  C catalyst end temperature. For example at the gas inlet to a TVA converter. A simplification [166] can be used which can be integrated analytically when the ammonia kinetics are approximated by a pseudo-first-order reaction [159–161]. 3 Ammonia. the apparent activation energy and reaction order. are rather troublesome and time consuming even for a fast computer. Mathematical models for calculating these effectiveness factors involve simultaneous differential equations. the economics of the total process are determined considerably by the performance of the ammonia catalyst [174]. 167–173]. it directly fixes vessel and exchanger design in the synthesis loop. the pore effectiveness factor E is a function of the so-called Thiele modulus m [162]: E¼   3 1 1  m tnhm m ð9Þ The Thiele modulus m is defined by m¼ deff 2 rffiffiffiffiffiffiffiffi kv Deff ð10Þ 153 where deff effective particle diameter Deff effective diffusion coefficient of ammonia in the catalyst particle reaction rate constant referred to a unit of kv particle volume tnh hyperbolic tangent The practical application of kinetic equations to the mathematical calculation of ammonia synthesis converters is described in [143. SV ¼ 15000 h1. High catalyst activity at the lowest possible reaction temperatures in order to take advantage of the favorable thermodynamic equilibrium situation at low temperatures. Ammonia content in the bulk stream (1) and in the catalyst pores (at r ¼ 0. as adopted by various research groups [51.4 MPa. a yield of 45 vol % ammonia can be expected with the same approach to equilibrium. and refrigeration requirement. recycle gas flow. according to the equation: r ¼ kv ðcNH3. 2. it determines the operating temperature range. 7) [51]. 2 R ¼ 5. As a result. and energy consumption for synthesis gas production and purification. and capital cost.

19). Cs Be. 8–9). Te F. The ammonia synthesis catalyst problem has been more intensively studied than the catalysis of any other industrial reaction. Pb. 5. and so to a premature plant shutdown. it must be kept in mind that the effect of poisons. Y. is so scarce that. Tl Sn. in 1910. From these experiments came a series of technical findings. Th Nb. In assessing the newly developed catalyst systems recommended for operation at very low temperatures (see Section 5. For example. metals or metal alloys are suitable as ammonia catalysts. La. or catalyst poisons Catalysts I II III IV V VI VII VIII Ce and rare earths (Ti). As. a reliable primary raw material source. Metals or metal compounds for which the chemisorption energy of nitrogen is neither too high nor too low show the greatest effectiveness (Figs. 179]. Mg.1. MITTASCH et al. Zn B.5. oxygen compounds. concerning the relationships between catalytic effectiveness and the strength of the nitrogen bond and reducibility. I activation or inactivation in doubly promoted systems.4). catalyst life was a big issue.154 Ammonia. Because of the high and increasing world demand for ammonia. denotes molecule. 3. (Mol. Zr. Ba. Insufficient pressure and abrasion resistance may lead to an excessive increase in converter pressure drop. Ni.1. Long life. K. Production Processes process (see Sections 5.1. S. because the catalysts in these plants showed a markedly reduced life owing to the severe operating conditions. Effectiveness of various elements as catalysts. U Poisons Cd. U (Mn). (Zr) (V) (Cr). as a precautionary measure for this option. At BASF A. mechanical disintegration during operation along with oxygen sensitivity thwarted the industrial application of uranium carbide catalysts [175]. for example. Mechanical Strength. Rb. Figure 8. Ti. promoters. for example. 3 Table 6. W. mol denotes mole) . above all those from the transition-metal group [177] (Table 6). Ru. (Ir) Promoters Li. so the magnetite-based catalyst proved suitable for industrial use. conventional iron catalysts achieve service lifetimes up to 14 years. [178. The rate constants of ammonia decomposition (A) on and the ammonia synthesis capacities (B) of metals as a function of DH00 . Re Fe. The experiments were finally brought to an end in 1922 after a total of 22 000 tests.3). in which up to 1911 more than 2500 different formulations were testet in more than 6500 runs. Os. Ca. C P. They tested almost all elements of the periodic table for their suitability as ammonia catalysts [7. In principle. Bi O. the necessary downtime for removing. may become more severe as temperature declines (see Fig. which was planned as the first industrial catalyst. Na. In older high-pressure plants (60 – 100 MPa). In modern single-train ammonia plants. Ce and rare earths Si. Mo. Sr Al. BASF had secured almost the total world supply [175]. which is determined essentially by resistance to thermal degradation and to irreversible poisoning (see Section 5. 176]. started a tremendous program. Mo. or relating to the mechanism of opposing Vol. Ta Cr. Br. replacing. Co. and 6.2). W. and reducing the catalyst had a considerable effect on the ammonia manufacturing cost. Se. 2. osmium. For example. 4. Cl. (Rh).

The catalytic activity of iron was already known well before the advent of industrial ammonia synthesis. conditions of preparation (Section 5. Composition Table 8 gives a composition survey of commercial ammonia catalysts in the years 1964 – 1966.1). calcium was added as the third activator. mol denotes mole). V. MITTASCH in 1909 established that catalysts manufactured by reducing a magnetite phase were superior to those prepared from other oxides. Cd.1. Th.1. Sr. at some sacrifice in temperature stability and resistance to poisons.2) can differ greatly one from another. Ce. individual catalyst manufacturers now offer several catalyst types in various particle size distributions. a ruthenium-based catalyst promoted with rubidium has found industrial application. Os.2). Ir. W. Rb.1. 2. P. Li. Catalytic activity of carbon-supported metals promoted by metallic potassium as a function of DH00 . The principal component of oxidic catalysts is more or less stoichiometric magnetite. 20 kPa of pN2 (Mol. Effect of various elements or their oxides on the activity of iron catalysts in ammonia synthesis a) b) c) Figure 9. Te. Ti. the highest . Er. Be. ammonia plant operating conditions and types of converters (Section 6.3. Bi. Classical Iron Catalysts From the early days of ammonia production to the present. S. in oxidic and prereduced states. Cr. U. Ba. as well as HABER and OøRDT [181]. Mn. conducted the first catalytic synthesis experiments with iron at atmospheric pressure. Ca.3). Y. Production Processes 155 Table 7. Sm. J. The basic composition of iron catalysts is still very similar to that of the first catalyst developed by BASF. which transforms after reduction into the catalytically active form of a-iron. Zr negative: As. the only catalysts that have been used have been iron catalysts promoted with nonreducible oxides. Na. Development work in the United States from 1922 can be found in [184]. Nb. The iron catalysts promoted with aluminum and potassium oxides proved to be most serviceable [183]. Mo. Thus. 5. PERMAN [180]. Later. Si oxides [176] (Table 7). Fe3O4 . NERNST [182] used elevated pressures of 5 – 7 MPa. Tl. Hg.1. Sn. Co. 3 Ammonia. To some extent even today. Pure iron showed noticeable initial activity which.Vol. however. denotes molecule. Ni. Zn doubtful: Au.1. could be maintained for longer operating periods only with extremely pure synthesis gas. For industrial catalysts. Pt.1. Pd. The highpurity gas of modern processes and the trend to lower synthesis pressures especially favor the development of more active and easily reducible types of catalysts. La. A) The rate of isotopic equilibration of N2 at 623 K. The degree of oxidation of industrial catalysts has a considerable influence on their catalytic properties. 80 kPa of total pressure 5. The ammonia synthesis catalyst problem could be considered solved when the catalytic effectiveness of iron in conversion and its onstream life were successfully and substantially improved by adding reduction-resistant metal positive: Al. Cl. Recently. Onstream life and performance were enhanced considerably by optimizing the component ratios (Section 5. Mg. B) The rate of ammonia synthesis at 523 K. Cu. Sb. F. B. Modern catalysts additionally contain other promoters that were present in the older catalysts only as natural impurities from the raw materials. Br. RAMSAY and YOUNG used metallic iron for decomposing ammonia. Pb. Ta. Nd. and catalyst particle size and form (Section 5. K. C.

96 3.95 3.54 2.7 2. Examples of commercial ammonia catalysts from the years 1964 – 1966.07 32.5 69. Nature of the Surface of Commercial Iron Catalysts. .11 platinum [191].66 4 4 4 5 – 11 2.50 0.67 0.7 Cr2O3 1.68 1.6 60. potassium. 3 Table 8.8 0. In general.91 31.55 0.85 1.58 1. as has Grande Paroisse [196].47 57.18 39.2 36. the catalysts contain varying quantities of the oxides of aluminum. ICI [195] has developed a cobalt-containing catalyst.3 66.08 1.85 3.30 2.10 1.0 23.59 0.54 0. potassium.56 0.2 66.9 88. beryllium [189].81 2.65 0.12 3 1.35 0.67 3. To obtain optimal catalyst composition. the pores represent 44 – 46 % of the volume of a catalyst granule [1].23 – 0. Patents recommend adding sodium [188].3 90.90 2.00 2.95 3.40 0.09 – 0.43 4. Freshly reduced commercial iron catalysts that contain aluminum.35 0.1 0.63 0.4 68.64 0.20 38.9 90.15 0. mm Bulk density.65 0.66 4. careful control of the manufacturing process.6.05 Cr2O3 – – – 0. Values for the composition in weight %.5 – 0.42 0. or Figure 10. magnesium.8 66.80 2.29 1.15 2.32 1.16 3. the pore distribution curve (Fig.30 2.0 70.35 3.9 4 2 normal 2 2 HT 2 prereduced 3 4 4 prereduced 5 6 (1964) 6 (1966) 7 prereduced 8 9 10 11 normal (1964) 11 (1966) 11 normal (1964) 11 (1966) 11 HT 11 prereduced 12 13 14 69.14 0. calcium.40 0.3 0.3 3.94 0.5 0. and silicon as promoters. the so-called inner surface.15 ammonia yields are observed with an Fe(II) – Fe (III) ratio of 0.42 3.0 0.8 – 4.43 0. which determine the oxygen content.94 2.58 3.18 62.10 2.0 65.37 0.27 58.1 cm3/g.50 0.55 0.80 2.60 1.20 1.57 0. Besides a maximum at a pore radius of about 10 nm that originates on reduction of the Fe3O4 (magnetite) phase of the nonporous oxidic catalyst.10 0.2 49.43 0.18 4.85 2.4 70.9 35.97 54.77 1.38 23.80 0.86 0.35 32. The pore volume measures 0.9 g/cm3. 55].0 0. vanadium [190].28 0.156 Ammonia.35 0. The surface of the walls of the pores.12 3.86 3– 5– 5/5 2– 2– 2– 9 10 2.1 71. 2. is necessary.5 66.30 0.3 84.13 2. Catalysts patented by Lummus [193] and Ammonia Casale [194] contain cerium as additional promoter.55 2.28 0. amounts to about 15 m2/g.89 0.34 2.53 59.70 56. accordingly.85 2.25 3.65 2.22 22.22 56. the spaces between them form an interconnecting system of pores.0 68. with an apparent density of 4.58 0.94 3.43 0.5 0.40 0.95 38. type Fe total FeO Fe2O3 Al2O3 MgO SiO2 CaO K2O Other Particle size. especially the melting conditions.62 3.7 68.17 1.80 1.52 1 – – – – – – 0. kg/L 1 68.57 0.5 66. The numbers at the beginning of the lines are keyed to the catalyst origin Origin.37 2.8 0.60 38.70 0. 11) generally shows a peak at 25 – 50 nm that is formed on reduction of the wustite phase [51.73 2.6 71.47 6.0 2.00 0.75 0.62 35.30 32.56 0.71 2.10 1.30 1.01 1.27 0. and calcium oxides as basic promoters consist of approximately 30-nm primary crystallites. about the degree of oxidation of stoichiometrically composed magnetite [185–187] (Fig.14 33.27 2.70 52.58 0.09 0.61 2.84 0.70 2. Production Processes Vol.26 0.55 0. Reference [192] describes cesium-containing catalysts.9 2.50 0.97 0.70 1.85 60.13 0.4 MnO – – – – – – – – – – – 2 4 6 6 6 2 33.90 2.57 0. uranium [232]. Dependence of the ammonia yield on the degree of oxidation of the iron in the unreduced catalyst – – – – – – 4 10 10 10 10 4 2.45 0.46 0. 10).0 1.73 3.

Large.0 41.0 1. Numerical values in atomic % [44] Fe Volume composition Surface composition before reduction Surface composition after reduction 40.0 157 The free iron surface of the reduced BASF catalyst [44] and Topsøe catalyst KM-I [56] comprises only a fraction of the total surface. 56]. There is also evidence that the basal plane of many platelets has the Fe(111) orientation [47. probably as a mixture of the silicate and ferrite [46]. 57–63]. as could be deduced from the results of prior investigations [51. Production Processes Figure 11. 845] of S€ udchemie is iron-based but uses wustite instead of magnetite – which previously was considered undispensible for the production of industrial ammonia catalysts – has an improved pore structure and higher specific surface area. Pore size distribution of a commercial catalyst after reduction at various temperatures [55] The novel AmoMax catalyst [844.5 K 0. although with low concentration [44. Auger electron spectroscopic (AES) measurements on an industrial catalyst (BASF S 6-10) have shown that a significant enrichment of the promoters into the surface results using the unreduced as well as the reduced catalyst [44] (see Table 9). apparently homogeneous regions that have originated from reduction of Fe3O4 crystallites alternate with nonhomogeneous regions that are formed by the reduction of FeO crystals or consist of amorphous phases [55]. With methods such as scanning transmission electron microscopy (TEM) and electron microdiffraction a textural hierarchy has been modeled. 3 Ammonia.0 4. about 1 wt % of the alumina also remains statistically distributed in the form of FeAl2O4 molecular groups built into the a-iron lattice of the reduced catalyst [64.7 40. 65]. Extensive studies in the last decade have provided a more refined picture of the morphology of the active catalyst (reduced state) and its precursor (oxidic state).7 4. and in the reduction process a further subdivision of the slabs into even smaller platelets might occur. Auger spectroscopic investigations on reduced BASF and Topsøe catalysts reveal large local differences in composition [44.Vol.0 17. According to [55. which act as spacers and ‘‘glue.0 27.’’ separating neighboring platelets and thus providing voids for the interconnection of the pore system.0 11. covers about 20 – 50 % of the iron surface. essentially at the grain boundaries. is relatively homogeneously distributed over the iron area of the surface. into separate regions. Table 9. . Composition by volume of an industrial ammonia catalyst in comparison to the surface composition before and after reduction (an approximately 104 cm2 size typical surface). Calcium oxide segregates.2 8. a correlation exists between the distribution of the potassium and that of aluminum and/or silicon.1 10. This texture is stabilized by structural promoters. This structure is already preformed in the preparation of the catalyst precursor. The composition of the outermost atomic layers of the pore walls deviates considerably from the overall average concentrations. 55].7 53. After reduction. The aluminum oxide promoter exists partly in the form of larger crystallites and. moreover. A review is given in [49]. 2.35 Al Ca O 2. According to [44] the potassium. 49]. Macroscopic particles in the reduced catalyst are confined by fracture lines running through a system of blocks consisting of stacks of slabs in parallel orientation. in the form of a K þ O adsorbed layer. 56].6 36.

187.and temperature-resistant catalysts containing up to 3. A graphic picture is conveyed in [202] of how the activity of a quadruply promoted (4 % Al2O3 . 0. a multitude of structural and electronic promoters has been investigated. The effect of a given promoter depends on concentration and on the type of promoter combination and the operating conditions. 2. such as Sm2O3 [205]. needs a higher reduction temperature than aluminum oxide-promoted iron catalyst [217]. Silicon dioxide additions shift the optimum potassium oxide concentration to higher values [200]. Under normal operating conditions [14 – 45 MPa. In striving to improve the activity or stability of iron catalysts. 216]. 0.3 – 5. the preferred catalysts contain 2. For higher operating temperatures. 12 B).5 % SiO2. 3 concentrations have an especially strong influence. For example. especially the reaction temperature and the synthesis gas purity [190. the opti10 000 – 20 000 m m mal activity corresponds to a composition of 2. 204]. Magnesium oxide addition now shows a favorable effect.0 % Al2O3. the Bulgarian catalyst K-31 contains 3. 12 C) or poisoned with 2000 cm3 water vapor per cubic meter of gas at 550  C (Fig.8 – 1. 12). 0. 0. Ho2O3.8 % SiO2. The ICI catalyst with composition 5. such as Al2O3.3 % CaO. 208]. for example. and 0. 2.0 % Al2O3. besides the usual additives.1. Promoter oxides that are reduced to the metal during the activation process and form an alloy with the iron (see also Section 5. The structural promoters.2 % CoO. classical Casale plants.2 % SiO2 (Fig. contained 1. 200.0 % Al2O3 . such as Al2O3.0 % MgO. 0. 1 % CaO.8 % K2O. Production Processes Influence of the Promoters.14 % SiO2 and 1. An industrial catalyst for operating temperatures up to 550  C is stabilized against deterioration by 2 – 5 % V2O5 besides 3. Raising or lowering the concentration of a particular oxide causes a reduction in activity. said to be thermally stable up to 650  C.5 – 4. Among those in use industrially. 3 3 1 h (STP)]. 380 – 550  C. among them rare-earth oxides [203. the optimum composition shifts to higher Al2O3 and SiO2 and lower K2O and CaO concentrations. Reducing the synthesis pressure and/or the synthesis temperature should enable application of the Lummus [193.9 % CaO.4 % MgO. 1.8 % K2O. 215.2 % MgO.5 % CaO. 1 % K2O. 213]. produce a high inner surface during reduction and stabilize it under thermal stress by restraining iron crystallite growth [83. 2. cobalt is of special interest [207.5 – 3. Dy2O3. If before the test the catalyst is overheated at 700  C for 72 h (Fig.5 % CaO. 12 D). Less active but more poison.3) are a special group. lower the rate of reduction [49. which operated at up to 80 MPa (800 bar) pressure and in which catalyst end temperature reached 650  C (see for example [1]). For ammonia plants operating at pressures up to 35 MPa (350 bar).6 % magnesium oxide were recommended for older plants. 0 – 1.9 % Al2O3. and Er2O3 [206]. such as the alkali oxides. However.2 – 0.57 % K2O. 214] and Ammonia Casale [194] cerium-containing catalysts. 0. 209–212].0 – 2.5 – 1.5 % Al2O3. 2.5 – 4. and the destructive effect with decreasing atomic radius [202]. catalyst end temperatures of 520 – 530  C maximum.0 – 3. 2. Changes in the potassium and aluminum oxide Vol. still higher V2O5 contents are recommended. enhance the specific activity (based on a unit surface) of iron – alumina catalysts. 202. they reduce the inner surface or lower the temperature stability and the resistance to oxygen-containing catalyst poisons [200. 0. and with highly purified synthesis gas. is substantially more active than the conventional cobalt-free catalysts [195. In the alkali-metal series. and 1. and a natural content of about 0. the promoter effect increases with increasing atomic radius.7 % K2O [190].5 % CaO.158 Ammonia. The effect of the promoters on the rate of reduction and the temperature required for reducing the iron oxide phase is also significant in industrial practice. The ability of the various metal oxides to create a high specific surface decreases in the following order [199]: Al2 O3 > TiO2 > Cr2 O3 > MgO > MnO ¼ > BeO CaO > SiO2 So-called electronic promoters.2 % K2O. 1 % SiO2 ) catalyst changes with varying promoter concentration and operating conditions (Fig. An older Norsk Hydro catalyst.5 % SiO2 [187]. and 0 – 1. 198]. remainder Fe3O4.2 % K2O. 201]. Promoters can be arranged in different groups according to the specific action of the metal oxides: Structural stabilizers. Magnesium oxide-activated iron. 2. Greater . Adding magnesium oxide decreases the catalyst performance.

The action of the so-called structural promoters (stabilizers).. B) Concentration of promoters. C) Overheating to 700  C with increasing promoter concentrations. there exists a close connection with the mechanism of the reduction .Vol. Early work [221] referred to the rough parallels between the reducibility and the thermal stability of catalysts. 3 Ammonia. such as Al2O3. 2. at 500  C. According to [227]. Mechanism of the Promoter Effect. the solubility limit in the magnetite mixed crystal is a maximum of 7. referred to iron.5 % FeAl2O4 . 222–224]. 226]. whereby only the portion dissolved in the magnetite phase appears to be responsible for the specific promoter action of alumina [57. D) Poisoning with water at increasing promoter concentrations differences in reducibility have also been observed in commercial catalysts with similar chemical composition [218] and in connection with particular oxide phases. 3 % Al2O3. The solid solutions of Fe3O4 and the spinel FeAl2O4 have a miscibility gap below 850  C [225]. Dependence of the catalyst activity on various factors A) Concentration of impurities. Production Processes 159 Figure 12. i. Higher alumina contents lead to separation into two phases. such as CaFe3O5 and FeO [218–220]. is closely associated with their solubilities in the iron oxide matrix of the unreduced catalyst or with the capability of the regular crystallizing magnetite to form solid solutions with iron – aluminum spinels [1.e. All published experience appears to demonstrate that it is not possible to combine in a catalyst high thermal stability with easy reducibility and high activity at low temperatures. Hence it may be advantageous to use a combination of active and thermallyresistant catalysts in the same converter. 58.

forms poorly reducible intermediate layers of calcium ferrite and silicates [55. the emerging K2O migrates to the iron crystallite surface. 230]. While doing this it reacts with the more or less homogeneously distributed aluminum (silicon) compounds. The unique texture and anisotropy of the ammonia catalyst is a thermodynamically metastable state. Production Processes which consists schematically of the following partial steps [228]: 1. 65. in the presence of SiO2. with formation of water vapor and release of electrons 2. on cooling the magnetite melt. In the reduced catalysts. Therefore. it segregates between the iron crystallites [45. (See also [37. potassium associates partly with the alumina in the surface. One may also presume that by partial neutralization of the ‘‘acid’’ components by calcium. The promoting effect of potassium seems to be based on two factors which probably act simultaneously. Another theory is based on the observation that during reduction part of the alumina precipitates with other promoters into the surface of the iron crystallite in a molecularly dispersed distribution [60. the potassium exists as a K þ O adsorption layer that covers about 20 – 50 % of the iron surface [44]. But the assumption that this will happen on a molecular Vol. 230]. 62] and so possibly prevents sintering together at high operating temperatures. According to [61. As indicated by the strong . It tends to stretch the magnetite lattice [37].and iron-rich regions were found [44]. where an FeAl2O4 molecule occupies seven a Fe lattice positions [37]. In this way. Sc2O3 . Formation of metallic iron nuclei by combination the electrons with Fe2þ ions 3. during reduction. 90]. 3 level on each basic structural unit is not true. According to [234]. In the reduced catalysts. more potassium is made available for activating the iron [143]. Potassium is likewise scarcely soluble in magnetite because of its ionic size [37]. however. Thus the primary function of alumina is to prevent sintering by acting as a spacer.4. 231] or in small islands [56]. Calcium oxide. 238]. partly as KOH with iron [838]. One mechanism is the lowering of the activation energy for the dissociative adsorption of nitrogen [36. about 30 nm.1. an analogous effect is to be expected with Cr2O3. the diffusion rate of the iron ions in the magnetite lattice is low. small iron crystallites. etc. In the main. 2. The appearance of a K2Fe22O34 phase besides an unidentified phase. it separates at the grain boundaries as CaFe3O5 (at very rapid cooling rates) [218] and. 235]. has been proved [233]. Impurity stabilization (structural promotion) kinetically prevents the transformation of platelet iron into isotropic crystals by Ostwald ripening [47]. 55]. 219]. Phase-boundary reaction of hydrogen with oxygen ions of the magnetite lattice. Hence. 81. According to this concept. 44]. It was found that the enhancement of the catalysts’ specific activity by potassium oxide is accompanied by a decrease in the electron work function [235–237]. This ‘‘patchy’’ monolayer of alumina acts like a ‘‘spacer’’ between iron atoms of neighboring crystallites and prevents sintering by means of a ‘‘skin’’ effect [65]. which also acts as a structural promoter [55] has a limited solubility in magnetite. it is distributed over the iron phase.) Insofar as small crystals of nonreducible oxides dispersed on the internal interfaces of the basic structural units (platelets) will stabilize the active catalyst surface Fe(111). The explanation is based on an electrostatic model [40. In the presence of dissolved aluminum ions. at not too high a temperature. [64. 227. separate potassium. In the unreduced catalysts. Diffusion of Fe2þ ions and electrons to the nuclei and growth of the nuclei to iron crystals of various size A more detailed discussion of the reduction mechanism is given in Section 5. The aluminum probably remains partly in the iron crystallite in the form of very small FeAl2O4 areas statistically distributed over the lattice [64.160 Ammonia. form with correspondingly large specific surfaces. nucleus formation proceeds rapidly relative to crystal growth. 46. and in part it may also contribute to stabilizing the Fe (111) faces [50. the paracrystallinity hypothesis will probably hold true. the stabilizer function of alumina reduces to paracrystalline lattice defects.

The negative effect of K2O concentrations higher than about 0. the recrystallization-promoting effect of higher K2O concentrations may be attributed to a lowering of the portion of alumina dissolved in the magnetite phase [233]. NH3 2. Catalyst performance 2. 7 m.58 % has not been explained unequivocally [83]. A nitrogen molecule adsorbed near such a site will experience a more pronounced back-bonding effect from the metal to its antibonding p orbitals.06. [240]. there is a considerable electronic charge transfer to the substrate.Vol. the pressure drop and the risk of destructive fluidization of the catalyst increase (Fig. 14). For processes operating at pressures of 25 – 45 MPa (250 – 450 bar) and at space velocities of 8000 – 20 000 m3 m3 h1 (STP) a grain size of 6 – 10 mm is preferred. Ammonia. 8 – 15 mm or 14 – 20 mm. 233]. which. An extensive review on promoters can be found in [41]. With increasing potassium concentration. hence. reaction pressure 27. practically speaking. [44]. this manifests itself by the increasing size of the average iron crystallite or the decreasing specific surface in the reduced catalyst [200. 13). which would exist in molten form at operating conditions [234. Since potassium oxide prevents the formation of solid solutions between alumina and magnetite to a certain extent [241]. 25 MPa. reaction temperature 450  C . 3 decrease in the work function upon potassium adsorption. is about 1 – 2 mm (Fig. 234].1. Influence of the particle size on the ammonia production (BASF catalyst). 838]. however. which creates a Md – Kdþ dipole. with decreasing particle size. Production Processes 161 Figure 13. p. CH4 10 From the standpoint of space – time yield. Depth of the catalyst bed. which avoids hindering of nitrogen adsorption by blocking (poisoning) of the catalyst surface by adsorbed ammonia molecules [34.2. This will increase the bond strength to the metal and further weaken the N – N bond. Pressure drop in the catalyst bed for various catalyst particle size ranges. 316]. 2. Larger granulations. for example. as can be seen from a further reduction of the N – N stretching frequency [239]. Pressure drop Figure 14. SV ¼ 12 000 m3 m3 h1 (STP). Particle Size and Shape The choice of particle size and shape of commercial ammonia catalysts is determined mainly by two factors: 1.1 MPa. are used only in plants where the lowest possible 5.59.55. it is desirable to use the finest possible particle. Remarks in [234] and [242] reveal another possible interpretation: the K2O located at the phase boundary surface and not bound to acid or amphoteric oxides may be converted by water vapor concentrations over 102 ppm in the synthesis gas into potassium hydroxide or by hydrogen into potassium and potassium hydroxide. gas composition (vol %): N2 20. from [1]. potassium oxide ought to improve the catalyst performance less at low than at higher operating pressures [135 p. The other effect consists of lowering the adsorption energy of ammonia. Ar 5. H2 60.

only a surface layer of the catalyst grains. As an example. which operate at comparatively low gas velocities [243]. 245]. in lay-out calculations it is customary to employ an effective particle diameter.5 5. L is equal to the diameter of a sphere with a volume equal to the (average) volume of the particles.5 4.2 1. 15) [326].5 – 3 or 2 – 4 mm) with optimal use of the converter volume. for example with a shape factor of 1. Comparison of the Ammonia Casale spherical catalyst and irregularly shaped catalyst [213] .5 – 3 1 – 1. if the particle size increases from about 1 to 8 mm.5 – 8 3–6 1.5 7. Figure 15. 2. Effect of catalyst size on catalyst volume Catalyst size classification. mm Approximate equivalent particle diameter. have so far been unsuccessful [244. which were explored especially in the Soviet Union.0 1. To allow for the influence of various particle shapes and size distributions within a defined sieve fraction. mm Relative catalyst volume. According to a patent by Chemie Linz AG [253]. regular shapes have the advantages of greater abrasion resistance and lower pressure drop (see Fig. 3 Table 10.5 4. Table 10 shows the relation between the catalyst size classification. The diameter deff is defined as the ratio of equivalent diameter L and a form factor y. Radial-flow converters and the horizontal crossflow Kellog converter (Fig. with a shape factor close to one. Two effects cause the low production capacity of coarse-grained catalyst: first. as nominal size. and y is the average ratio of the particle surface to the surface of a sphere of equal volume. participates in the reaction. Vol. allow the use of small granulations (1. At the high reaction rate typical for the converter inlet layer. deff. Fluidized-bed processes.7 2.5. because this proceeds only by slow diffusion through the pore system.3 95 90 82 79 An irregular grain shape. preferably 5 – 10 mm long and 1 – 2 mm thick (broad). In catalyst zones in which the ammonia formation rate is so high that the allowable temperature limits are exceeded. On the other hand. the inner surface decreases from 11 – 16 m2/g to 3 – 8 m2/g [251]. this induces a severe recrystallization [1].2 100 92 – 88 – 80 – 77 – – – – – 6. large grain size retards transport of the ammonia from the particle interior into the bulk gas stream. the catalyst particle ought to be 2 – 20 times as long as it is broad.5 2. the equivalent particle diameter. The second effect is a consequence of the fact that a single catalyst grain in the oxidic state is reduced from the outside to the interior of the particle [246]: the water vapor produced in the grain interior by reduction comes into contact with already reduced catalyst on its way to the particle outer surface. about 1 – 2 mm thick. 48).162 Ammonia. has a more favorable effective activity for the individual particle and for radial intermixing of mass and heat in an industrial converter [252] than a more cubic or spherical shape. % 6 – 10 4. The effect is very significant. Slow ammonia diffusion inhibits the rate of reaction. and the percentage saving in catalyst or converter volume relative to the 6 – 10 mm standard size [213]. Production Processes pressure drop is essential because of very high gas velocities. it may be advantageous to use coarse particles for suppressing the reaction.

magnetite is melted with the additives at high temperature (> 1600  C) and the melt is cooled. however. In fact this is only the catalyst precursor which is transformed into the active catalyst composed of a-iron and promoters by reduction with synthesis gas. Swedish charcoal iron). This is activated in the well-known manner by reductionresistant metal oxides. Impregnating the pore surface of prereduced passivated catalysts is a possibility for incorporating promoters into iron ammonia catalysts. Complex iron cyanides were decom- Ammonia. for example. and reduction – influence the quality of the finished catalyst (Fig. Catalyst-Precursor Manufacture The term ‘‘ammonia catalyst’’ commonly refers to the oxidic form consisting of magnetite and oxidic promoters. synthetic magnetite. such as bentonite [262]. a binding agent. macroporous catalysts. Magnetite leads to especially efficient catalysts. similar to those obtained by exchange of magnesium ions by iron ions in the surfaces of magnesium hydroxy carbonate crystals [270. The application of macroporous catalysts ought to be especially useful for very low synthesis pressures and in plants in which large catalyst particles must be used for reasons of low pressure drop. The cooled melt is ground to the proper granulation and reduced with hydrogen – nitrogen mixtures. Various manufacturing techniques have been proposed [254–263].3. broken. the powder is pelletized. such as cerium nitrate [194]. and its electrical conductivity allows the use of economical electrical melting processes. alternating-field heating [277] has been attempted also. As an example. with subsequent calcining and reduction [267–270]. was burned to Fe3O4 in a stream of oxygen. the performance of the macroporous Topsøe catalyst KMG 6 mm at 5 MPa synthesis pressure is said to be at least equivalent to KM I 1. Repeatedly described as a means of manufacture. After water is added and. This process was largely replaced by melt processes in which natural or. have not gained industrial importance. 3 The advantages of regular catalyst shapes and the need to compensate for the abovedescribed negative effects of larger grain size by a system of macropores in the oxidic and reduced catalyst stimulated various attempts to manufacture shaped. A process developed by Farbenfabriken (formerly Friedrich Bayer) had only local significance.g. In 1996 the prices of commercial ammonia catalysts were about 2 $/lb (3. 265]. they are among the least expensive catalysts. Therefore. 2. finally to a iron. is coprecipitation of the catalyst components. treatment with ultrasound [274. very small (under 10 nm) iron particles are obtained with high specific iron surfaces [270].23 e/kg) for prereduced. With magnesium oxide as support. melting. together with the activators. mechanical treatment [276]. . The first effective catalysts were made by the oxygen-melt process. and ground to powder. The purest possible iron (e. 275]. Operating conditions in the individual manufacturing steps – proportioning and mixing the raw materials. less frequently. Granulation and sintering techniques have been used for the preparation of shaped macroporous iron catalysts.1. 271]. by way of example. together with the additives. Production Processes 163 posed thermally in the presence of hydrogen. Fe3O4 . was melted electrically or in electric arc furnaces [186.5 $/lb (10. The so-called Mont Cenis process employed such catalysts [266]. The reduction step is very important for catalyst performance.. The pellets subsequently are dried and sintered in an inert atmosphere at higher temperatures (about 1350  C). The superiority of the catalyst manufacturing processes that use a molten iron oxide stage is mainly due to the fact that above 1000  C in air. is the thermodynamically stable oxide phase of iron [7.5 – 3 mm and distinctly superior to KM I 6 – 10 mm [264]. from aqueous solutions of the metal salts. if required. which. although only in the scientific literature. Improving the performance and life of industrial catalysts by radioactivity and X-rays [273]. crushing or if necessary grinding and preforming. magnetite. usually in situ. or high-frequency. or a promoter salt. A United Kingdom patent [272]. cooling. The hydrodecomposition proceeds via the carbide and nitride. 16) [174]. claims catalysts manufactured by impregnating the reduced catalysts with cerium salts. For example. 5.Vol. 278].58 e/kg) for oxidic and about 5.

4. Induction furnaces are optimal for the melting operation. Very slow cooling results in a more cubic chip. With falling temperature. In practice. 17). . Melting is accomplished in electrical resistance or induction furnaces (arc furnaces in the past) operating at 1600 – 2000  C. such as magnesium oxide. there may exist relationships between the melt cooling rate. are not reduced [1]. Vol. Therefore. slow cooling is avoided. it is well mixed. The walls of these furnaces should consist of a weakly basic tamping material indifferent to the melt. A homogeneous distribution of the promoters in the magnetite melt and a degree of oxidation at or under that of stoichiometric magnetite should be obtained. as far as possible. which can be lowered with magnetic separators [279]. Since the melt is held in constant turbulent motion by the magnetic field produced in the primary coil. which is also an activating component of the catalyst [280]. Ammonia catalyst manufacture The raw materials – usually. Quenching or fast cooling in thin sheets leads to a less abrasion-resistant. Many ores have too high a content of free or bound silica. 5. The magnetite is converted into a highly porous. lime. The promoters. It is claimed to be advantageous to bring the promoters into the melt as common chemical compounds that are isomorphous with magnetite [282]. plant cost and power consumption are higher.5). c) Melt temperature 1800 – 2000  C (slow cooling) Another important factor in catalyst manufacture is the melt cooling rate. high surface area. In comparison to the most frequently used resistance furnaces. potash. b) Melt temperature 1800 – 2000  C (rapid cooling). and the reducibility of the catalysts.164 Ammonia. but with inferior catalyst quality (Fig. Their good temperature control permits accurate adjustment of the degree of oxidation.1. sharp-edged chip after crushing. and alumina – must.1. 2. even for short melt times. be free of catalyst poisons (see Section 5. by rapid cooling of the melt the activator oxide distribution can be frozen in a condition corresponding to that of a higher temperature [283]. the appearance of certain phases. Production Processes Figure 16. Effect of the melting temperature and rate of cooling of the melt on the activity of ammonia catalysts a) Melt overheated to 3500  C (rapid cooling). natural magnetite. 3 Figure 17. which is affected by the design and dimensions of the ingot molds. Catalyst Reduction The reduction of oxidic catalyst is generally effected with synthesis gas. 17). with the exception of cobalt. According to [218]. highly catalytically active form of a-iron. both the solubility of the activator oxides (see page 31) in magnetite and the rate of adjustment to the new phase equilibrium decline. This is said to be promoted by initially overheating to temperatures up to 3500  C [281] (Fig.

The influence of the hydrogen/nitrogen ratio during reduction on the catalyst performance after reduction is discussed in [287]. The influence of the reduction conditions (gas flow rate. and at not too high pressures (7 – 12 MPa in low-pressure.Vol. the reduction should be carried out at high gas velocities [about 5000 – 15 000 m3 m3 h1 (STP)]. 3 To ensure maximum effectiveness of the catalyst. the manufacturers hold these in strict secrecy. long reduction times are needed at low temperatures and low pressures with a consequential loss of production. although a slow induction period starts somewhat lower. The chemical reaction creates an iron(II) ion concentration gradient in the solid. 25 – 30 MPa in highpressure plants) to hold the exothermic formation of ammonia under better control during the reduction. microscopy. This is made possible by the structural defects of the wustite. The minimum temperatures necessary for reduction are somewhat different for the various catalyst types. the water content of the gas effluent from the catalyst should not exceed 2 – 3 g/m3 (STP). Metallic iron is formed from wustite by direct chemical reaction controlled in the initial phase by the reaction rate (activation energy ca. the reduction temperature is raised stepwise by using the exothermic heat of ammonia formation. Under these conditions. at the lowest temperatures sufficient for complete reduction. The reducibility of industrial catalysts is dependent on both the combination of promoters and the degree of oxidation. According to [218]. Above all. 65 kJ/mol) and in the final stage by diffusion processes involving hydrogen and water on the reaction site: FeOþH2 !FeþH2 O 2. Production Processes 165 ly. the rather considerable differences in the reduction rates of commercial catalysts with similar compositions may be attributed to differences in manufacturing methods or operating conditions. When the reduction of the oxidic catalyst is carried out in the production plants. Common- Ammonia. The precipitation of further wustite nuclei on the magnetite/wustite reaction interface seems to be effected by ion/ electron diffusion processes rather than by direct contact of magnetite with hydrogen [292]: O2 þH2 !H2 Oþ2 e Fe3 O4 þFe2þ þ2 e !4 FeO The topotactic reduction process leads to a core and shell structure which is visible under the optical microscope and is shown . Some older publications deal with the influence of catalyst granulation on the optimum reducing conditions [285]. The FeO (wustite) phase is reduced faster and at lower temperatures than the Fe3O4 (magnetite) phase [218]. Catalysts conventionally employed in medium-pressure plants may be reduced from about 340 to 390  C. nitrogen content in the hydrogen in the range 0 – 100 %) on the production capacity of an ammonia catalyst has been investigated [293]. Directions for reduction in multibed converters that combine fineand coarse-grained catalyst appear in [286]. In practice. Generally. This gradient leads to a rapid diffusion of iron(II) ions from magnetite through wustite to the chemical reaction interface. temperatures above 440  C are required to complete the reduction. High temperature and high water vapor partial pressure markedly accelerate premature catalyst aging by recrystallization. The gas/solid reaction between magnetite and hydrogen has been studied in great detail by rate measurements. a summary is given in [49]. temperature in the range 300 – 600  C. where they are reduced and precipitated as iron nuclei. Therefore. As a rough guideline. a defined reduction procedure must be followed. and X-ray diffraction [288–291]. 2. a synthesis converter with a fresh load of oxidic catalyst attains its full production capacity in 4 – 10 d. The progress of the reduction is controlled according to the catalyst temperature and the water concentration by means of the synthesis gas flow. depending on its size and operating pressure. it is important to hold the partial pressure of the resulting water vapor as low as possible and to insure that the water vapor does not come into contact with regions that have already been reduced. On the atomic scale the reaction is controlled by two processes: 1.

introduced on the market some years ago. such as reducing the risk of damaging the catalyst during activation by too high a local concentration of water. Information on the reduction kinetics. but the shell and core model is also valid for commercial polycrystalline catalysts [294. A more detailed atomistic picture leads to the assumption that there is no homogeneous topotactic reaction interface. as well as the roughly 20 % lower bulk weight (which reduces the design loadings and costs of the internals of large converter units). the quantitatively lower yield of aqueous ammonia solution (which can be added to the production). including industrial catalysts. Ammonia formation begins at substantially lower temperatures. 3 Figure 18. The somewhat inferior mechanical strength is a disadvantage that requires special care when a charge is being loaded into the converter. so that altogether the downtime of a production unit is reduced markedly. the method recommended by BURNETT . have gained a considerable market share. 49]. make using prereduced catalysts increasingly attractive.166 Ammonia. Mechanism of catalyst reduction [42] a) Reducibility of catalyst under standard conditions as a function of its porosity. 246–250]. Usually. When removed from the hydrogen – nitrogen atmosphere at low to moderate pressure in the producing furnace. According to this concept the active catalyst should not grow as a shell around a precursor core but as a core within an oxidic matrix. especially in single-train plants. Newer findings seem to question the shell and core model with the topotactic reaction interface [97]. Production Processes Vol. Reactivating such catalysts usually takes only 30 – 40 h. Figure 18 (b) shows the wustite/magnetite interface as observed by electron microscopy [49]. 2. This concept was developed for single-crystal magnetite grains. Prereduced. Prereduced catalysts have the full pore structure of active catalysts. the prereduced catalysts are pyrophoric and must be stabilized before transport and installation by passivating the surface. c) Reaction interface schematically in Figure 18 (a). although the pore surface has been oxidized to a depth of a few atomic layers to make these catalysts nonpyrophoric. This and further advantages. can be found in [47. in spite of higher prices. Stabilized Catalyst Types. b) Core and shell structure of catalyst. On account of the simplifications involved this model should be regarded as a formalistic approach to describe the reaction kinetics rather than a mechanistic approximation.

The equivalence of H2O. prereduction. In contrast to temporary poisons.46 0. Oxygen-containing compounds such as H2O. The experimentally determined effect of water vapor concentrations up to about 30 ppm on the activity of a commercial catalyst (BASF S 610) at 30 MPa is evident from Figure 19. set up a rate equation for ammonia synthesis [297. 5. 303]: H2 OðgÞþ3  2 H  þO where * denotes a surface site.63 0. A more recent investigation [299–301] proposed multiplying the rate equation by a correction factor 1  Q. reduction. passivating.1.5. CO2 and O2 [304] with respect to their poisoning effect has been confirmed. pH2O/pH2 and falls with increasing temperature. Some authors assume a different route for the formation of adsorbed atomic oxygen [302. Ammonia. Corresponding to the adsorption equilibrium.39 0. The reducible oxygen content of the prereduced catalyst ranges between 2 and 7 %. CO2. Table 11. For gaseous poisons in the synthesis gas. lead to the same degree of poisoning. Under the assumption of a displacement equilibrium in accordance with ðN2 Þads þH2 Ogas þ2 H2 gas ðOÞads þ2 NH3 I. a distinction can be made between permanent poisons that cause irreversible damage to the catalyst and temporary poisons which lower the activity while present in the synthesis gas. These substances can be minor gaseous constituents of the synthesis gas or solids introduced into the catalysts during the manufacturing procedure. CO. including a discussion of the most important literature in this field.14 . which is proportional to pH2 O= pH2 [296]. derived from impurities in the natural magnetite from which the catalyst is made. Catalyst Poisons The activity of an ammonia synthesis catalyst may be lowered by certain substances. That is. the activity of a damaged catalyst may be practically completely restored by reduction with clean synthesis gas. and reactivation.20 0. Production Processes 167 100 ppm of O2 or CO2 and 200 ppm CO or H2O. Temperature.1 – 0. and the use of high-purity promoters. Detailed data on the manufacturing steps most important to the catalyst performance.74 0. 2. The damage depends approximately linearly on the quantity of adsorbed water taken up by the catalyst pffiffiffiffiffiffiffiffiffiffiffi ffi pffiffiffiffiffiffiffiffi[295]. and O2 are the most common temporary poisons encountered in ammonia synthesis.Vol. permanent poisons can be detected by chemical analysis. These latter should not play a major role with catalysts from manufacturers of repute and are not discussed in detail in this section because of the proprietary nature of the production processes. A. appear in [1]. CO. where Q ¼ aþbTþcTlnXH2 O and XH2 O is the molar fraction of H2O.24 0. C values for the ammonia synthesis rate equation Oxygen Compounds have a reversible effect on iron catalysts at not too high temperatures. The melting process itself may also contribute to minimizing the content of some minor impurities. the degree of poisoning therefore rises with growing partial pressure ratio. for example. SMIRNOV et al. General measures to avoid this sort of contamination include selecting a rather pure magnetite. Part of this is only loosely bound and is removed in reactivation even below 200 – 300  C.  C Catalyst Fe þ Al2O3 Fe þ Al2O3 þ K2O 400 425 450 475 500 0. the application of pretreatment processes.28 0. 3 is used. presumably because as soon as they enter the catalyst bed they rapidly and completely transform into H2O [1].2 MPa (1 – 2 bar) and up [284].12 0.17 0. 298] that takes the effect of water vapor into consideration over a wide range of temperature and pressure: v¼ k1 pN2 k2p2NH =p3H2 ð11Þ 3 ðp2NH3 =p2H2 þCpH2 O =pH2 Þ1=2 and found the values of C listed in Table 11. The reduced charge is treated with nitrogen containing 100 – 1000 ppm oxygen at 50 – 70  C (maximum 95  C) and a pressure of 0. Equivalent concentrations of oxygen compounds. commonly referred to as poisons.

Activity of BASF ammonia catalyst S 6–10 in a commercial converter after 14 years of operation . For a carbon monoxide content of 5 ppm. 305]. operating periods of up to 14 years can be achieved for a converter charge without significant loss of activity (Fig. As already mentioned in Section 5. 20). Reversible effect of increasing water vapor concentrations in the synthesis gas on the activity of industrial ammonia catalysts With continuing exposure oxygen compounds also cause irreversible damage to the catalyst activity that is causally linked with growth of the iron primary crystallite [301. Figure 19. ~ after 14 years operation . generally recommended for modern plants.1.168 Ammonia. the production declined by about 15 % per month. This is probably one of the main causes of the decline in converter performance over the course of the catalyst operating life. the concentration and combination of promoters affect the degree of irreversible damage. This must be considered in the choice of catalyst for a particular plant. they determined about a 4 – 5 % decrease in activity per year. in contrast to reversible poisoning. the greater is the harmful effect of oxygen compounds [306]. Sulfur. no serious deterioration of the catalyst performance is observed after a month of operation. That is. catalysts partially poisoned with hydrogen sulfide cannot be regenerated under the conditions of industrial ammonia synthesis. and Arsenic Compounds. The performance of a catalyst operated at 570  C is about 35 – 40 % under that of a catalyst charge operated at 520  C. for example. 2. at ¨ sterreihigh temperatures. With the highly purified synthesis gas of modern synthesis processes (with final gas purification by methanation the carbon monoxide level is lowered to below 5 ppm). Production Processes Vol. There are indications that these permanent poisons exert the most detrimental effect when present as hydrogen compounds and are less harmful in higher oxidation states [307]. This damage depends on the water-vapor partial pressure and is especially serious. In a pilot plant.1. For example. fresh catalyst. Phosphorus. Compounds of phosphorus and arsenic are poisons but are not generally present in industrial syngas. Figure 20. temperatures above 500 – 520  C must be avoided in order to achieve a converter charge operating period of more than 2 – 3 years. the higher the temperature. Linz. Corresponding to the data. estabchische Stickstoffwerke (O lished that at 30 MPa and a water-vapor content of 250 ppm. O ¨ SW). is more tightly bound on iron catalysts than oxygen. Sulfur. then even at CO concentrations of 20 ppm in the recycle loop gas. The influence of the operating temperature is evident from the data. occasionally present in synthesis gases from coal or heavy fuel oil. If the temperature is kept at this level. 3 they established that above all.

Like oxygen.25 mg S/m2 is sufficient. and major progress was achieved over the years. 2. in terms of activity. It is therefore very important to use an oil with low sulfur content in ammonia plants. In ammonia synthesis itself considerable progress was made in converter design and recovery of the reaction energy at high temperature. On cracking the oil to lower molecular mass hydrocarbons. The deactivation effect is based at least in part on the formation of alkali chlorides that are volatile at the upper synthesis temperatures.2 wt % ought to be sufficiently low.2. Concentrations of about 0. Under similar poisoning conditions. most of the sulfur already has been taken up in the gas inlet layer. To reach this goal a synthesis catalyst with a volumetric efficiency some two orders of magnitude greater than magnetite would be necessary. 5. 0. Pure iron and catalysts activated simply with alumina chemisorb S2N2 or thiophene when treated with concentrations of H2S that lie below the equilibrium for the FeS bond. The permanent poisoning effect of chlorine compounds is two orders of magnitude worse than that of oxygen compounds. A catalyst sulfur content of several 100 ppm suffices to impair its activity [1]. sulfur may reach the ammonia converter in various forms.2. especially between those containing or free of alkali and alkaline earths. a sulfur content of the oil of 0. 301]. a value under 0.Vol. but there has been no substantial improvement in the catalyst since the 1920s.5 mg of sulfur per m2 of inner surface or free iron surface. In industrial plants.5 – 1 mg S/m3 (STP)). the sulfur contained in the compressor oil constitutes the main danger. sulfur promotes recrystallization of the primary iron particle. because otherwise too low an ammonia concentration would result. 309].1. thus cancelling the energy saving from synthesis gas compression. Ammonia.16 – 0.1 ppm are viewed as the uppermost allowable limit in order not to affect adversely the life of ammonia catalysts [310]. From the vast amount of experimental and theoretical studies of the iron catalyst one can conclude that there is only limited potential for further improvement. and additional energy would be needed for recovery. say. although in a few cases a pressure as low as 80 bar has been used. Further information on catalyst poisoning is given in [300. Other Catalysts 5. alkaliand alkaline earth-containing industrial catalysts adsorb more H2S. a maximum of 0. For total poisoning. whereas FeS formed by treatment above 300  C with high H2S concentrations is reducible as far as the monolayer. The standard commercial iron catalyst still requires relatively high pressures (usually in excess of 130 bar). however. In some plants. this corresponds to monomolecular coverage [308. The monolayer is also preserved on reduction with hydrogen at 620  C. to compensate for the less favorable equilibrium situation much lower operating temperatures would be necessary. In spite of this. In a catalyst bed. General Aspects For a long time efforts to improve the efficiency of industrial ammonia production concentrated on synthesis gas production. Substantial energy savings would require lowering the synthesis pressure considerably. traces of H2S and COS may not be removed in the upstream purification steps and so may enter the converter with the make-up gas. If after mixing with the recycle gas the make-up gas first runs through an ammonia condensation stage in which the H2S and also to a certain extent COS are very effectively washed out by condensing ammonia. Otherwise. Process studies show an energy saving potential of about 1 GJ per tonne NH3 [836]. high temperatures (400 – 500  C) and large reactor volumes (more than 60 m3 for a capacity of 1500 t/d) to achieve good economics. sulfur is freed as H2S. Production Processes 169 Chlorine Compounds. However. 3 With regard to the sulfur bound on the catalyst surface. especially those still using reciprocating compressors. In modern plants designed with centrifugal compressors and in which the sulfur content of the synthesis gas is extremely low because of very effective purification (about 0. sulfur poisoning is of lesser importance than carbon monoxide and chlorine poisoning. However. . differences exist between the various types of ammonia catalysts. down to the synthesis gas production level.1 – 0.1 % is recommended [310]. they are more stable toward the action of sulfur and are partially regenerable [309].

2 Os 5. .2. as may be seen from Table 12 [311]. 5. Metals with Catalytic Potential Materials that show significant ammonia synthesis activity can be divided into three categories according to their ability to form nitrides: 1. though only in presence of alkali metal promoters. Vol. most metals have been tested. A special limitation until recently was the chemical reactivity of carbon supports. In a typical ammonia synthesis environment with high hydrogen partial pressure. Promoter localization with respect to metal sites and support sites. Most of the studies in the following years concentrated on the magnetite system in the sense of more fundamental and general catalytic research. Anion retention capability.2. Much of this work was performed in the early.6 Co 0. Of course. The properties of the supported catalyst will be influenced by several factors [120] . the use of a support material is the only viable option. which would lead to Table 12. Adequate surface of the carrier to achieve a reasonable metal loading. H:N ¼ 3:1) Mo 0. The only other catalyst system which exhibits a promising potential for industrial application is based on ruthenium [120]. . 323]. Platinum group metals: no stable nitrides (Ru.008 . Os. Metals likely to be present as nitrides under synthesis conditions (groups 3 – 6 of the periodic table) Of the platinum group metals only ruthenium and osmium show an activity superior to iron. this metal never became an industrial catalyst because of its limited availability and its dangerous properties. Dispersion stability by using a more active support with strong interaction between the support phase and the metal precursor. and tortuosity. for an expensive material such as the platinum group metals. 573 K. First of all iron is a cheap material and secondly by the incorporation of alumina a surface area similar to that attained in highly dispersed supported catalysts can be obtained. Rising energy costs since the mid-1960s have given a new incentive to the search for other catalyst systems with improved performance.36 Fe 0.68 Ni 0. A major advantage of graphite is its ability to stabilize high loadings of alkali metals. Re) 3. Too strong an interaction may cause difficulties in the metal reducing. and porosity must also be taken into account. pioneering studies in the BASF laboratories [175. The classical commercial iron catalyst is an unsupported catalyst. Co. Tc. Metals forming nitrides unstable under reaction conditions (Mn. such as number of active sites.4 Rh 0.04 Pd 0 Pt 0. Gas transport effects will be governed by pore size. These new efforts to find improved catalysts could use methods and knowledge of modern surface science as developed on the example of the magnetite catalyst. Fe. physical form. pore distribution. It is unlikely that the promoter is in metallic state as its high vapor pressure would probably lead to substantial losses under synthesis conditions. For the overall performance of potential catalysts in practical application additional factors.313 kPa. The first development which found commercial application was a cobalt-modified magnetite catalyst introduced in 1984 by ICI. Although osmium was the first active catalyst used by HABER in 1909 [312] in his laboratoryscale unit to demonstrate the technical viability of the high-pressure recycle process. 2. The interest therefore shifted to ruthenium.170 Ammonia. 176]. Ni. It is assumed that a charge transfer complex MþC is formed between the metal and the graphite. Ir. The most active ruthenium catalysts use a graphite support and alkali metal promotion.72 Ru 22. 128. Ammonia synthesis activity of metals supported on carbon with potassium metal promotion (mL NH3/ mL catalyst. either as primary components or as promoters. With similar kinetic characteristics its volumetric activity is about twice that of the standard iron catalyst. Structural sensitivity and nature of the nitrogen adsorption and dissociation steps could serve as guidelines [121]. preferentially with rubidium or cesium [319.52 Ir 0. . Pt) 2. Production Processes In the search for an alternative catalyst.6 Re 0. which plays a role in the catalyst preparation by impregnation of a support with metal impregnation of the support. 3 . the catalyst may also catalyze the methanization of carbon.

according to the patent example. 322]. but it can be avoided by careful heat treatment of the support above 1500  C [314]. 875]. For the special properties of ruthenium. its application for ammonia synthesis catalyst in [846]. 318]. A notable development for the magnetite system was the introduction of cobalt as an additional component by ICI in 1984 [320. ruthenium. the AmonMax-10 of S€udchemie which uses wustite instead of magnetite. The cobalt-enhanced catalyst formula was first used in an ammonia plant in Canada using ICI Catalco’s AMV process (later also in other AMV license plants) and is also successfully applied in ICI’s LCA plants in Severnside. As in the case of iron a clear structural sensitivity was found for rhenium but the role of promoters remains the subject of discussion. the rate-determining step in the ammonia synthesis reaction is the dissociation of the nitrogen molecule and the catalyst effectivity is determined in the first instance by the activation energy of the dissociation reaction. each with a nameplate capacity of 1850 t/d. 321]. The catalyst has a considerably higher surface area than the conventional catalyst and. In 1979 BP disclosed to M.3. the promoted ruthenium catalyst works best at a lower than stoichoimetric H/N ratio of the feed gas as shown in Figure 21. Topsøe has developed a ruthenum catalyst which . kinetic investigations are reported in [121]. In October 1990. irrespective of the catalyst. Tc. The only commercial catalyst is a cobalt containing magnetite [315]. There are also indications of structure sensitivity for cobalt and nickel. which is claimed to be 10 – 20 times as active as the traditional iron catalyst: The KAAP catalyst. The other common factor for the ammonia catalysis is the structure sensitivity of molecular nitrogen adsorption. The group of metals forming low-stability or unstable nitrides includes Mn. Commercially successful is a new type of iron-based catalyst. On account of its very strong ammonia inhibition rhenium is not an option. Indeed. Fe. promoter concentrations. The results of the intensive research in this field over the last decades demonstrate that. Production Processes 171 achieved for the magnetite system: optimization of manufacturing procedures. Ni. the others with the ruthenium – graphite catalyst.2. Kellogg started the commercialization of the Kellogg Advanced Ammonia Process (KAAP) using this catalyst [322]. The first layer of the four-bed reactor [841. only molybdenum is of some interest. and Re. after a tenyear test program. According to the patent [315] the new catalyst is prepared by subliming ruthenium-carbonyl [Ru3(CO)12] onto a carbon-containing support which is impregnated with rubidium nitrate. it should contain 5 wt % Ru and 10 wt % Rb. With this modified carbon material lifetimes of at least six years are expected [311]. can a sufficient overall reaction rate be expected. Production of synthetic wustite is described in [847]. Besides having a substantially higher volumetric activity.Vol. Kellogg a new catalyst composed of ruthenium on a graphite support [320. Under synthesis conditions it is present as a nitride with some ammonia formation activity and structural sensitivity [316]. Co. 5. It is also less susceptible to selfinhibition by NH3 (Figure 22) and has excellent low-pressure activity. The available data show that these conditions are fulfilled only for a limited number of metals: iron. Three ammonia plants in Trinidad. this phenomenon has been observed [313]. 331] is loaded with conventional magnetite catalyst. 3 destruction of the support. 2. Only if both conditions are favorable. This catalyst is already used in seven ammonia plants with a total capacity of 5600 t/d [843–845. and osmium. Commercial Ruthenium Catalysts Since the early days of industrial ammonia synthesis only minor improvements have been Ammonia. For a literature report on promoted iron catalysts see [848]. and particle size to give somewhat higher activity and longer service life. It was attempted to improve the activity of the classical magnetite catalyst by alloying with nickel or cobalt.W. use the KAAP ruthenium catalyst [840]. and other factors such as hydrogen and ammonia inhibition do not play a major role. Extensive literature on non-iron catalysts is given in [120. 121]. Of the group of metals forming stable nitrides. Molybdenum also seems to exhibit activity in biological nitrogen fixation [317] and is synthetically active at ambient conditions in the air-sensitive Glemser compounds [317. which have to be considered in handling these catalysts see [331].

presents an update of the state of the art from time to time. The complete process of industrial ammonia production may be subdivided into the following sections: A. More modern and comprehensive reviews of ammonia production technology can be found in [329–331. Synthesis gas production 1. a Stokes Engineering Publication. Of course. due to new applications in the electronic industry. Ammonia inhibition of Ru and Fe3O4 catalysts [120] The most fundamental changes over the years have occurred in synthesis gas production and . occasionally called ‘‘white graphite’’. 6.172 Ammonia. 3 whether the benefits of its use are sufficient to compensate the higher costs. In common with the iron catalyst ruthenium will also be poisoned by oxygen compounds. The potential for ruthenium to displace in the long run iron in new plants will depend on Vol. The journal Nitrogen. A discussion on ruthenium as ammonia synthesis catalyst with an extensive literature review is found in [866]. An overview over ammonia synthesis catalyst development history and newer research is given in [849]. Carbon monoxide conversion 3. Compression C. A Ba-Ru/BN catalyst proved completely stable in a 5000 h test at 100 bar and 550  C using a 3:1 H2 – N2 mixture [849]. 3. published by British Sulphur. Process Steps of Ammonia Production The term ‘‘ammonia synthesis’’ is increasingly used when referring to the total ammonia production process. Effect of H/N ratio on activity of Ru and Fe3O4 catalysts [120] uses boron nitride instead of graphite as support. Boron nitride. 841. 831]. they are an important consideration in the total process but can be determined properly only in relation to the total plant integration (see ! Ammonia. Feedstock pretreatment and gas generation 2. Production Plants. Synthesis conditions are no longer viewed in isolation. Ruthenium prices increased by a factor of four in 2000 to 170 $/oz. There is no industrial application so far. Gas purification B. is completely stable towards hydrogenation under all conditions relevant to technical ammonia synthesis. Production Processes Figure 21. 2. because of its structure similar to graphite. Chapter 1). the United States patent literature in the field from 1972 to 1980 is covered in [229]. A literature summary of ammonia production is contained in [327] and [328]. Ruthenium price development is occasionaly published in FINDS. Even with some further potential improvements it seems unlikely to reach an activity level which is sufficiently high at low temperature to allow operation of the ammonia synthesis loop at the pressure level of the syngas generation. Synthesis and purge gas management Figure 22. now named Nitrogen þ Syngas.

1 1. and so the manufacturing cost) largely depend on the raw material employed [339. 3 Ammonia.0 1. Therefore. The capital cost and the specific energy requirement (i. Table 14 shows the relative capital cost and the relative energy requirement for a plant with a capacity of 1800 t/d ammonia. CH4 . In North America. although strictly speaking a distinction should be made between gasification feed and fuel for energy generation.5 1. petroleum.  CH2. with 95 % of capacity. some progress has been made in converter design and optimization of heat recovery.3 2. carbon monoxide conversion. which would be only justified when electric power is generated from water power. 2. Table 14..15 1.. feed and fuel. may contain hydrogen (natural gas. air.6 . Table 13 provides an overview of the raw material sources (apart from water and air) for world ammonia capacity. Certain raw materials for synthesis gas production that were once of primary importance currently are used only under special economic and geographical circumstances (e. Production Processes 173 Table 13.e. only a short abstract is presented here.5 kWh/Nm3 H2) is used together with an air separation unit for the nitrogen supply the energy requirement amounts to 34 GJ per tonne NH3 when the electric energy is valuated just with the caloric equivalent. for its part. The investment could according to a rather rough estimate be about three times the investment for a steam reforming plant with natural gas. These include solid fuels. Reference [334] covers coke oven gas as a feedstock for ammonia synthesis and references [335–338] describe producing hydrogen by water electrolysis for ammonia production. Usually only the carbon-containing materials and hydrogen from other sources are regarded as raw materials in the narrow sense because of the abundance of air. the regional distribution is diverse. that. and a carbon-containing reducing medium. In case of electricty generation from fossil energy with 40 % efficiency the consumption figure is 85 GJ per tonne NH3. which generally supplies most of the hydrogen.Vol. For the natural gas based plant the current best value of 28 GJ per tonne NH3 is used. In the synthesis section itself. This trend is also expected to continue in the near future. natural gas from the Slochteren field in the Netherlands contains 14 % nitrogen. for example. which is 300 % of the consumption of a modern steam reforming plant [862].  CH) and nitrogen. Processes. Feedstock distribution of world ammonia production capacity 1962 Coke oven gas and coal Natural gas Naphtha Other petroleum products Total 1972 1983 1998 103 t N % 103 t N % 103 t N % 103 t N % 2800 7800 2050 2950 15600 18 50 13 19 100 4600 32100 10700 3600 51000 9 63 21 7 100 7200 66850 9050 7200 90300 8 74 10 8 100 16500 94300 7300 4400 122500 14 77 6 3 100 gas compression. China. natural gas dominates. In the EU. Relative ammonia plant investment and relative energy requirement for 1800 t/d NH3 Relative investment Relative specific energy requirement (based on lower heating values) Natural gas Naphtha Fuel oil Coal 1. 340]. coke oven gas. Synthesis gas preparation. 2.0 1.1. 6. for example. If water electrolysis (4. 86 % of capacity is based on natural gas and 8 % on naphtha [427]. Naturally.5 1. which provides all of the nitrogen. where 66 % of production is based on coal). Table 13 indicates that new ammonia plants are based almost exclusively on natural gas and naphtha. and water. naphtha.g. The raw materials are water. The term feedstock is often applied to the total consumption of fossil fuel. Synthesis Gas Production The goal is preparing a pure mixture of nitrogen and hydrogen in the stoichiometric ratio of 1 : 3. and gas purification for ammonia synthesis are treated in detail in the article ! Gas Production. and hydrogen produced by electrolysis.

In the partial-oxidation route less hydrogen is produced in the primary gasification step and the raw synthesis gas has a rather high CO content. some nitrogen. Chapter 2). 3 6.174 Ammonia. COþH2 O CO2 þH2 DH 0298 ¼ 41 kJ=mol ð14Þ Although reaction in the right hand direction is favored by lower temperatures it is responsible for the initial carbon dioxide content of the raw synthesis gas. 486. It attains the theoretical maximum of 66 % with methane. oxygen. where air is used. any sulfur compounds present in the hydrocarbon feedstock have to be removed by hydrodesulfurization. In addition cracking reactions will occur on the catalyst. . Adsorption on activated carbon is an alternative when the feed is natural gas with a rather low sulfur content. usually the major constituent of natural gas. But for the different feedstocks there are some constraints on the applicability of the various gas generation processes. It yields a gas mixture made up of CO and H2 in various proportions along with carbon dioxide and.2). this reaction is carried out in a separate step over a different catalyst at a lower temperature than the preceding gasification step (Section 6. air. 5). Corresponding to Equation (6). Introduction. which gives rise to a simultaneous reaction according to Eq. C11) undergo reaction with steam over a catalyst according to Equation (5) which is usually called steam reforming. The positive enthalpy per mole of hydrogen therefore decreases as the proportion of hydrogen contributed from the feedstock itself increases. 1. 2. Thus for heavy feedstocks the only choice is noncatalytic partial oxidation.1. which would poison the sensitive reforming catalyst. however. An additional equilibrium reaction involved in any gasification process is the water gas shift reaction (7). Natural gas consists predominantly of methane and is therefore the most hydrogen-rich and energetically the best raw material for the steam-reforming route. which not only blocks the catalyst pores but also restricts interparticle flow. which. Steam Reforming Processes (see also ! Gas Production. The raw gas composition is thus strongly influenced by the feedstock and the technology applied. depositing carbon. commonly known as partial oxidation. These raw materials contain a substantial amount of sulfur and also minor quantities of heavy metals. generally with a combination of cobalt – molybdenum and zinc oxide catalysts [485. Any carbon containing feedstock will undergo a reaction according to Equation (5) or (6) or both simultaneously. is capable of processing any type of hydrocarbon feedstock. The catalytic steam reforming technology can only be applied to light hydrocarbon feedstock (up to naphtha) but not for heavy hydrocarbons such as fuel oil or vacuum residue. From Equation (5) it can be seen that in the steam reforming variant the proportion of hydrogen supplied by the feedstock itself increases with its hydrogen content. As the nickel-containing catalysts are sensitive to poisons. RSHþH2 !RHþH2 S ð15Þ H2 SþZnO!ZnSþH2 O ð16Þ The general overall reaction can be formulated as Cn Hð2n þ2Þ þn H2 O nCOþð2nþ1ÞH2 ð17Þ or more specifically for methane.1. or any combination of these is generally referred to as gasification. 564]. 7) proceeds. To maximize the hydrogen yield. The various commercial coal gasification processes may also be classified as partial oxidations. all carboncontaining feedstocks can be processed in a noncatalytic reaction with oxygen (together with a minor amount of steam for process reasons.1. Feedstock Pretreatment and Raw Gas Production The chemical reaction of hydrocarbons with water. ½CHx þH2 O COþH2 þx=2 H2 DH > 0 ð12Þ ½CHx þ1=2 O2 COþx=2 H2 DH < 0 ð13Þ Light hydrocarbons ranging from natural gas (methane) to naphtha (max. Production Processes Vol. The hydrogen – oxygen bond energy in water is higher than the hydrogen – carbon bond energy in the hydrocarbon. as: CH4 þH2 O COþ3 H2 DH ¼ þ206 kJ=mol ð18Þ Simultaneously to this equilibrium the water gas shift reaction (Eq.

Vol. 3

To introduce nitrogen to achieve the required
stoichiometric hydrogen/nitrogen ratio for ammonia synthesis, the reforming reaction is split
into two sections. In the first section, the primary
reformer, the reaction proceeds in indirectly
heated tubes filled with nickel-containing
reforming catalyst and is controlled to achieve
a partial conversion only [in conventional plants
65 % based on methane feed, leaving around
14 mol % methane (dry basis) in the effluent
gas]. In the following secondary reformer — a
refractory-lined vessel filled with nickel catalyst – the gas is mixed with a controlled amount
of air introduced through a nozzle (burner). By
combustion of a quantity of the gas the temperature is raised sufficiently (to about 1200  C)
that the endothermic reforming reaction is completed with the gas adiabatically passing the
catalyst layer. In this way the outlet temperature
is lowered to around 1000  C, and a residual
methane content of 0.5 % or lower (dry basis) is
attained in conventional plants [329, 331]. Nitrogen already present in the natural gas tends to
cause a reduced specific air ratio in the secondary reformer and a reduced secondary reformer
temperature rise. Therefore, to maintain the
same methane leak, the primary reformer exit
temperature must be increased.
The primary reformer consists of a multitude
of reformer tubes loaded with the nickel catalyst
(15 – 25 % NiO on a-aluminum oxide, calcium
aluminate, or magnesium aluminum spinel support) [841] in a furnace box in which the heat
needed for the reaction is transferred to the tubes
by radiation. The heat is generated in burners,
generally gas-fired, in the furnace box.
A special consideration is the lifetime of
the expensive reformer tubes, made of highly
alloyed chromium-nickel steel by centrifugal
casting, because under the severe reaction conditions the material exhibits creep which finally
leads to rupture [850, 867]. The time to rupture
for a specific material depends on the tube-wall
temperature and on the internal pressure. This
limits the reforming pressure, which to save
energy in synthesis-gas compression should be
as high as possible. As the reforming reaction is
endothermic and proceeds with volume increase the negative effect of a pressure increase
(lower conversion) has to be compensated by a
higher reaction temperature and hence higher
wall temperatures, but this is limited by the

Ammonia, 2. Production Processes

175

material. Another possibility to compensate is a
higher steam surplus (steam/carbon ratio), but
this is economically unfavorable. The furnace
box usually accommodates 200 – 400 tubes
(depending on plant capacity), 10 – 13 m long,
with an inner diameter of 75 – 140 mm and
a wall thickness of 11 – 18 mm. The standard
material for a long time was HK 40 (20 Ni/
25 Cr) but for replacements and new plants, HP
modified (32 – 35 Ni/23 – 27 Cr stabilized
with about 1.5 % Nb) is being increasingly used
on account of its superior high-temperature
properties [350]. With this latter tube material
a reforming pressure of 40 bar is possible at
outer tube-wall temperatures of around 900  C .
A further improvement are microalloys that
additionally contain Ti and Zr [331, 841, 863,
865].
According to the disposition of the burners
primary reformers can be classified as top-fired,
side-fired, terraced-wall, or, less common,
bottom-fired reformers [331, 841]. The steam/
carbon ratio used in modern commercial primary
reformers for natural gas is between 2.8 and 3.5,
and markedly higher for naphtha, for which an
alkalized nickel catalyst has to be used to prevent
carbon deposition, which causes catalyst deactivation and local overheating of tubes (hot bands
and hot spots). A special requirement for the
catalyst is a low content of silica, which could
be volatile under the hydrothermal conditions
and deposit downstream of the secondary
reformer at lower temperature, causing fouling
of the waste-heat recovery surfaces.
When higher hydrocarbons (naphtha) are
used, a so-called ‘‘rich gas stage’’ can be utilized
upstream of the primary reformer. In this, the
higher hydrocarbon – steam mixture is transformed at relatively low temperature (400 –
500  C) and steam – carbon ratios less than two
into a methane-rich gas. This is then converted
in the primary reformer under normal reforming
conditions. For this rich-gas stage, three processes are commercially available: the British
Gas Process [351], the BASF – Lurgi Process
[352–354], and the Japan Gasoline Process
[355].
This process has recently become the subject
of renewed interest for increasing the capacity of
existing natural-gas-based ammonia plants in
which the primary reformer has been identified
as bottle-neck. Under the name pre-reforming, it

176

Ammonia, 2. Production Processes

is installed up-stream of an existing tubular
reformer [356–363, 331, 841]. The natural gas
enters such a pre-reformer with a temperature of
530  C instead of being fed to the primary reformer tubes with the same temperature. A temperature drop of about 60 – 70  C occurs in the
catalyst bed due to the overall endothermic reaction. Medium-grade heat is used to reheat the exit
gas to the correct primary reformer entrance
temperature. This compensation heat may be
derived from a variety of sources, including flue
gas, process gas, or gas turbine exhaust.
Another possibility for reducing the load on
the primary reformer is to transfer part of the
conversion duty to the secondary reformer with
application of an super-stoichiometric amount
of air. This requires removal of the surplus of
nitrogen from the synthesis gas either ahead
of the synthesis loop (by cryogenic methods or
pressure swing adsorption) or by purge gas and
hydrogen recovery [382, 383]. In the extreme
case the whole reforming reaction could be performed without a tubular reformer by autothermal catalytic reforming in a design similar to a
secondary reformer. In this case it would be
necessary to use oxygen or oxygen-enriched air

Vol. 3

instead of air [329, 371, 384, 385, 841, 877, 878].
Unlike to a secondary reformer, which is fed with
partially reformed gas, having a substantial concentration of hydrogen, the autothermal reformer
(ATR) is fed directly with the hydrocarbon feedstock. Because of the higher heat of reaction in
the internal combustion (temperature >2000 C),
the flow conditions, heat release characteristics
and the risk of soot formation are very different
from the situation of a normal secondary reformer. Therefore special considerations in the design of burner and reactor are necessary. See also
! Gas Production, 2. Processes.
A recent development which avoids a fired
primary reformer is the exchanger reformer,
which with some simplification may be viewed
as tubular heat exchanger with the catalyst inside
the tubes, which are heated by the hot secondary
reformer effluent flowing on the shell-side. In
some designs the tubes may be open at the lower
end, in which case the gas flow on the shell side
consists of a mixture of the off-gases from the
secondary reformer and from the reformer tubes.
Commercially operating designs are the GHR
of ICI (Figure 23) [331, 386–389] and the KRES
of M. W. Kellogg [391–395, 841–843, 872]

Figure 23. ICI gas heated reformer
A) GHR; B) AGHR
a) Tubeside inlet; b) Tubeside outlet; c) Scabbard tube; d) Bayonet tube; e) Sheath tube; f) Shellside inlet; g) Shellside outlet;
h) Catalyst tube; i) Seal; j) Tail pipe; k) Catalyst; l) Refractory lining

Vol. 3

Ammonia, 2. Production Processes

177

Figure 24. Kellogg reforming exchanger System (KRES) [331]

(Fig. 24). Similar concepts are offered by other
licensors and contractors e.g., Braun & Root, or
Topsøe [331].
ICI has come out with a modified design, the
AGHR, with ‘‘A’’ standing for advanced. As
shown in Figure 23 B, the bayonet tubes are
replaced by normal tubes attached to a bottom
tubesheet using a special seal to allow some
expansion. In this way the delicate double tubesheet of the GHR is avoided. The seal which
prevents leakage of methane-rich gas to the
secondary reformer effluent flowing on the shell
side has a unique design which is subject to
patent applications of ICI. The AGHR will allow
a single-line concept for worldscale plants
whereas with the GHR several parallel units for
large plants would be necessary [331].
Because of the smaller size compared to a
conventional fired reformer considerable investment savings can be achieved. To close the
heat balance between the exchanger reformer
and secondary (autothermal) reformer, the latter
has to take on a higher reforming duty, which
may be achieved by using an over-stoichiometric amount of air or oxygen-enriched air. In
some configurations the exchanger reformer is
partially by-passed, part of the feed being fed
directly into the autothermal reformer.
Haldor Topsøe has developed an exchanger
reformer called HTER which may be used in
various process configurations as described in
[851]. The design may be also used as a convective reformer, called HTCR with a dedicated
burner.

A concept developed by Uhde goes a step
further in this direction: exchanger reforming and
subsequent noncatalytic partial oxidation, which
provides the reaction heat, are accommodated
in a single vessel. This combined autothermal
reformer (CAR) design, shown in Figure 25 was
operated in a demonstration unit producing
13 000 m3/h of synthesis gas [397–400].
A unique steam reforming process [364–366]
has been developed in Japan to the pilot-plant

Figure 25. Uhde combined autothermal reformer (CAR)
a) Sandwich type tubesheet; b) Enveloping tube; c) Reformer
tubes; d) Tubesheet; e) Refractory lining; f) Water jacket

178

Ammonia, 2. Production Processes

Vol. 3

stage. It reportedly can operate without upstream
desulfurization and should be able to gasify
naphtha, crude oil, and atmospheric or vacuum
residues.
For literature on steam reforming see
[329–333, 345, 367–373]; reaction kinetics and
thermodynamics [841]; for steam reforming of
naphtha, [376–378]; for steam reforming catalysts, [379, 380, 331, 381, 841, 852] for reformer
design, [331, 374, 375, 841]. An oververview of
the steam reforming technology, its historical
development, present state of the art, newer
developments and future perspectives together
with quotation of newest literature is given in
[850]. Detailed discussion on exchanger reforming and autothermal reforming is found in
[851].
Partial Oxidation. Hydrocarbons or coal
will react with an amount of oxygen insufficient
for total combustion to CO2 according to:
Cn Hm þn=2 O2 !n COþm=2 H2

ð19Þ

Cþ1=2 O2 !CO DH ¼ 123 kJ=mol

ð20Þ

In practical operation some steam must
always be added, the quantity depending on
feedstock and process configuration, so that the
following reactions proceed in parallel:
Cn Hm þn H2 O!n COþðnþm=2ÞH2

ð21Þ

CþH2 O!COþH2 DH ¼ þ119 kJ=mol

ð22Þ

As the overall reaction is exothermic no
external heat supply is necessary. Since in some
processes with coal feedstock (e.g., the Lurgi
Process) the reaction according to Equation (15)
may proceed to a considerable extent, they are
more often referred to as coal gasification rather
than as partial oxidation, but this is just a matter
of definition.
Certain processes have achieved particular
significance. The Texaco and Shell processes
can handle fuel oil, vacuum residues, and coal.
The Lurgi process handles lump coal, operates at
2.5 MPa, the Koppers – Totzek process operates
on coal dust at atmospheric pressure.
Partial Oxidation of Hydrocarbons. The
two dominant processes are the Texaco Syngas

Generation Process (TSGP) and the Shell Gasification Process (SGP). In both the reaction is
performed in an empty pressure vessel lined with
alumina. The reactants (oil and oxygen, along
with a small amount of steam) are introduced
through a nozzle at the top of the generator
vessel. The nozzle consists of concentric pipes
so that the reactants are fed separately and react
only after mixing at the burner tip or in the space
below. The temperature in the generator is
between 1200 and 1400  C. Owing to insufficient mixing with oxygen, about 2 % of the
hydrocarbon feed is transformed into soot, which
is removed from the gas by water scrubbing.
Depending on the process configuration the gas
is either cooled by quenching or in a waste-heat
boiler. The TSGP and SGP are rather similar,
they mainly differ in the nozzle design, soot
removal and recirculation, and process gas
cooling. The reaction pressures may be as high
as 80 bar; there are no mechanical or material
limitations to raising the gasification pressure
further, but with respect to the overall ammonia
process this might be beyond the energy optimum because of the increasing energy demand
for nitrogen and oxygen compression. Maximum
raw gas generation capacity of a single generator
corresponds to about 1000 t/d ammonia. Worldscale ammonia plants based on partial oxidation
exist in Germany, India, China, and other countries [390]. Further information is found for the
TSGP in [346–349, 411, 412, 414–416], for the
SGP in [396, 402–410, 417]; see also ! Gas
Production, 2. Processes.
Partial Oxidation of Coal. So far the
Koppers – Totzek, Texaco and Lurgi gasifiers,
and probably the Winkler process in some smaller installations, have been used in ammonia
plants, but the successful demonstration of the
Shell process in other applications makes it a
potential candidate for ammonia production,
too. Additional processes in different stages of
technical development are the HTW and the
Dow process. Information on the status and the
development in the gasification of coal can be
obtained from [418–421, 423–426, 428]. A
special case is China, where a number of small
plants with a capacity of 30 – 80 t/d still produce their synthesis gas with the today largely
outdated water-gas process which operates at
atmospheric pressure. Coke or anthracite is

The temperature in the lower section of the bed is around 1000  C.Vol. 431–435] used in several ammonia plants in China. As a result of this lower temperature the raw gas has an increased content of impurities such as tars. The British Gas/Lurgi Slagging Gasifier [420.g. 831] is being tested in a 48 t/d pilot plant. a new concept developed by AECI Engineering. Depending on feedstock and process technology. is today still in use in some smaller plants (e. In addition the methane content is relatively high (up to 10 – 15 %). all carbon oxides must be removed from the raw synthesis gas of the gasification process. this gas contains 10 – 50 % carbon .2. The process actually can use any sort of coal and can handle ash contents higher than 30 %. 457. In a further development (HTW process) by Rheinbraun it has been tested in a demonstration plant with lignite at 10 bar [459. To overcome the disadvantage of atmospheric pressure operation.1. so that purification and conditioning of the raw gas is a rather elaborate task. in China). 2. India. The gasifier is a slender column with a square crosssection. The process can handle bituminous coal and lignite. In its coal gasification process [420. 456] operates without a grate with withdrawal of the liquid slag. 453. and at the top where the raw gas exits about 600  C. is introduced immediately at the head of the burners. 451–455. followed by a water scrubber to remove carbon and ash traces from the raw gas and to effect further cooling. 6. and carbon scrubber are especially adapted to deal with the ash and slag introduced with the bituminous coal feed. dry coal dust is introduced via lock hoppers into the reactor vessel operating at 20 – 40 bar. Dry coal dust is fed to the two (sometimes four) burners of the gasifier. The Texaco Coal Gasification Process [420. The Advanced Coal Gasification Process (ACGP) [462]. The classic Winkler gasifier. a version was developed capable of operating at 25 – 30 bar. With reversed flow pattern in the gasifier (from bottom to top). together with a small amount of steam. Carbon Monoxide Shift Conversion As ammonia synthesis needs only nitrogen and hydrogen. Shell has completely departed from the concept of its process for partial oxidation of heavy hydrocarbons. Ash with only 1 % of residual Ammonia. Pulverized coal and oxygen are injected near the base of the gasifier through eight burners using a proprietary feed technique which employs a special pump. which operates at atmospheric pressure. The residence time is less than 1 s and the temperature is 1500 – 1600  C. 458] performs the reaction in a moving bed. and the mixture enters the reaction zone with high velocity. An aqueous slurry containing 60 – 70 % coal is fed by reciprocating pumps to the generator at a pressure of 20 – 40 bar. The upper part is made of finned tubes which are welded together and are circulated with water by thermosyphon action. The Koppers – Totzek Process [429.. The combustion area is lined with heat resistant ceramic material. usually operating at 25 – 30 bar. quencher. So far no commercial installation exists but it is claimed that one unit can produce the synthesis gas for 750 t/d ammonia. is an entrained gasification process at atmospheric pressure. Kynoch Ltd and Babcock Wilson. This Prenflow (pressurized entrained flow) process [436. and South Africa. 460]. Liquid slag is withdrawn from the reactor bottom. 443–450] is rather similar to the Texaco partial oxidation process for heavy hydrocarbons. The Lurgi Dry Gasifier [420. and some higher hydrocarbons. Waste-heat boiler. 422]. 3 reacted intermittently with air and steam in a fixed bed. Oxygen. A block diagram showing steam reforming and partial oxidation together with the further steps needed to transform the raw gas into pure make-up gas for the synthesis is shown in Figure 26. 437–442]. phenols. The gas leaving the top of the reactor vessel is cooled in a waste-heat boiler. The heat produced by the exothermic reaction of coal and air in the ‘‘blow phase’’ is stored in the fixed bed and provides the heat needed for reaction of coal with steam in the ‘‘run phase’’ [24. Crushed coal with a particle size of 4 – 40 mm enters the top of the gasifier through a lock hopper and is evenly distributed over the cross-section of the coal bed surface by a distribution disk equipped with scraper arms. Production Processes 179 carbon is removed at the bottom of the gasifier by a revolving grid with slots through which steam and oxygen are introduced. operates practically at atmospheric pressure.

2.2 vol % at 220  C and 0. it is favored by lower temperatures. 7). which shift the equilibrium to the right-hand side. As the process configuration and catalysts are to some extent different for steam reforming and partial oxidation. Quasi-isothermal reactors have been developed in which cooling tubes run though the catalyst layers. it is practically independent of pressure. To keep the temperature low the heat of reaction must be removed in appropriate way and to achieve a sufficient reaction rate effective catalysts have to be applied. the carbon monoxide serves as reducing agent for water to yield hydrogen and carbon dioxide.12 vol % at 200  C for a steam/gas ratio of 0. Alternative process steps for generation and purification of synthesis gas monoxide and also varying amounts of carbon dioxide.4. Shift Conversion in Steam Reforming Plants. the gas from the secondary reformer. cooled by recovering the waste-heat for raising and superheating steam. 0. with intermediate heat removal between the individual catalyst beds in which the reaction runs adiabatically. In the water gas shift reaction. After a temperature increase of . 3 Figure 26. Production Processes Vol. enters the high-temperature shift (HTS) reactor loaded with an iron – chromium catalyst at 320 – 350  C. traditionally known as carbon monoxide shift conversion (Eq. but as an exothermic process. In the traditional plant concept.180 Ammonia. Even with a low excess of steam in the gas. The process is therefore performed in steps. they are treated separately here. In this way not only is the carbon monoxide converted to readily removable carbon dioxide but also additional hydrogen is produced: COþH2 O CO2 þH2 DH ¼ 41:2 kJ=mol ð23Þ As no volume change is associated with this reaction. the equilibrium concentrations of CO are low. for example.

7 mol % (dry basis) is achieved. but recently radial gas flow configurations have been chosen in some instances. 469. amines (mainly methylamine) are formed from the methanol and traces of ammonia originating from the secondary reformer and the HTS. 3 around 50 – 70  C (depending on initial CO concentration) and with a residual CO content of around 3 % the gas is then cooled to 200 – 210  C for the low temperature shift (LTS). Decreasing the steam surplus lowers the oxygen to carbon ratio in the HTS to such an extent that the atmosphere can reduce magnetite partially to metallic iron. and iron carbides will be formed. The LTS catalyst. The reaction heat can be removed by use of a tube-cooled reactor raising steam or heating water for gas saturation to supply process steam in the reforming section (Linde LAC. .Vol. but nowadays usually with LTS catalyst [483]. The catalyst properties are influenced far more by the formulation and manufacturing procedure [472] than by its chemical composition. Unlike sulfur poisoning.1 ppm. In some ammonia process schemes operating without a secondary reformer and applying pressure swing adsorption (PSA) for further purification (KTI PARC) only a HTS is used. but this is of greater importance in partial oxidation processes and less for the practically sulfur-free steam reforming gas. The classical HTS iron catalyst is resistant against sulfur compounds. The copper oxide is reduced in situ with hydrogen and a carrier gas (usually nitrogen) to form fine copper crystallites on which the activity depends. supplied in pellets like the HTS catalyst. the H2S causes deactivation of the copper by sintering. 470]. A relatively new process concept is the intermediate temperature shift (ITS) [475] which performs the shift conversion in a single step. ICI Catalco LCA). 20 – 30 % zinc oxide. Traces of chlorine compounds [482]. which are effective Fischer – Tropsch catalysts that lead to the formation of some methane and higher hydrocarbons [331. In the unreduced state the HTS catalyst is iron (III) oxide (Fe2O3) containing additionally 5 – 10 % chromic oxide (Cr2O3). it is reduced more or less stoichiometrically to the composition of magnetite (Fe3O4). usually present as H2S. New catalyst types with increased activity and higher selectivity have reduced the problem. The resulting carbon is deposited within the catalyst particles causing their disintegration. The tendency for methanol formation increases with decreasing steam/gas ratio [477]. Steam surplus is not only necessary for thermodynamic reasons but also to suppress undesirable side reactions. chlorine is more diffusely distributed over the whole catalyst bed by migration as volatile zinc and copper chlorides. but even with such low concentrations. a methane slip of only 0. the catalyst is slowly poisoned. In a consecutive reaction. 474]. formerly loaded with ZnO. These pollutants are removed from the process condensate by steam stripping and ion exchange. During operation. consists of 40 – 55 % copper oxide. As chemical composition and formulation of the LTS catalyst are very similar to methanol production catalysts. The ZnO adsorbs the sulfur and it finally transforms into Ammonia. the balance being alumina. Sulfur. In addition the Boudouard reaction can occur under these conditions. The poisoning process moves through the catalyst as a relatively sharp front and can be seen in the change of the catalyst temperature profile over time [473. When the ZnO is exhausted in a given layer of the catalyst. 2. has to be below 0. In a new plant using the spiral-wound Linde reactor [476]. Production Processes 181 bulk ZnS. small quantities of methanol are formed and are found in the process condensate after cooling the LTS effluent.1 – 0. This catalyst is active in the temperature rage of 300 – 500  C. The catalyst is based on a copper – zinc – alumina formulation and optimized for operating in a wider temperature range than the standard LTS catalyst. Further purification is performed by PSA. which is carried out on a copper – zinc – alumina catalyst in a downstream reaction vessel and achieves a carbon monoxide concentration of 0. Generally the shift conversion reactors have an axial gas flow pattern. which may be introduced with the natural gas or more often with the process air to the secondary reformer.3 vol %. may also deactivate the LTS catalyst by accelerating the sintering of the copper particles. The LTS catalyst is protected by a guard bed. Newly introduced HTS catalysts with additional copper promotion suppress this side reaction [471] and are therefore less sensitive to lower steam-to-gas ratios. Changing the guard bed more frequently prolongs the service life of the main LTS catalyst bed. Byproduct formation is higher with fresh catalyst and declines with operating time.

the gas may contain a rather high amount of sulfur compounds (mainly H2S with smaller quantities of COS). The sulfur compounds (see Section 6. 329. the CO content is much higher. Gas Purification upstream of gasification to avoid poisoning of the sensitive reforming catalysts. CO2 loading characteristics of various solvents Shift Conversion in Partial Oxidation Plants. 841].1. residual carbon monoxide.1. 563] is present under reaction conditions in sulfidized form and requires for its performance a sulfur content in the gas in excess of 1 g S/m3. In the chemical solvents the carbon dioxide becomes fixed as a chemical compound. This cobalt – molybdenum – alumina catalyst [342. In the early days of ammonia production water. In another process variant the sulfur compounds are removed after shift conversion. First. In further purification. The CO2-laden solvent is flashed. As this is an essential part of the steam reforming process it is treated in Section 6. Production Processes Additional literature on shift conversion can be found in [331–333. Vol. carbon dioxide. in some cases in excess of 50 %. which are removed as described below. at higher partial pressures the physical solvents (according to Henry’s Law. 344. served as solvent in a oncethrough process without regeneration and recycling.3) can be removed ahead of the shift conversion to give a sulfur-free gas suitable for the classical iron HTS catalyst.1. This is usually performed by hydrodesulfurization and adsorption of the H2S by ZnO. The classical method for CO2 removal is to scrub the CO2 containing synthesis gas under pressure with a solvent capable of dissolving carbon dioxide in sufficient quantity and at sufficient rate. which needs heat for its decomposition. 343. the high initial carbon monoxide concentration means that the reaction must generally be performed in steps. Figure 27 shows the loading characteristic for various solvents. At low carbon dioxide partial pressures. The total sulfur contained in the coal and hydrocarbon feedstock is converted in gasification to H2S and a smaller amount of COS. As the standard iron catalyst can tolerate only a limited amount of sulfur compounds. The raw synthesis gases from partial oxidation of heavy hydrocarbons and coal differ mainly in two aspects from that produced from light hydrocarbons by steam reforming. the so-called dirty shift catalyst is used in this case. the loading is approximately proportional to the CO2 partial pressure) have a higher loading capacity than the chemical solvents. which thus has to deal with a high-sulfur gas. 343. second. usually in countercurrent in a column equipped with trays or packings. Reaction temperatures are between 230 and 500  C.8 % in a single step in a large hydrogen plant by using a quasi-isothermal reactor (e. and the spent scrubbing liquid is subsequently heated and regenerated in a stripping column before being recycled to the pressurized absorption column.g. Today a variety of solvents are used and they can be categorized as physical or chemical solvents. and sulfur compounds (only present in the synthesis gas from partial oxidation) have to be removed as they are not only a useless ballast but above all poisons for the ammonia synthesis catalyst. 3 6.182 Ammonia. with intermediate cooling. 461. 479–481. depending on the feedstock composition. 463–468. In contrast steam reforming requires removal of sulfur from the natural gas and light hydrocarbon feedstocks Figure 27. It has been reported that the CO content can be reduced from 50 to 0. .3. the chemical solvents absorb substantially more carbon dioxide than the physical solvents. for which the solubility approaches a saturation value. Irrespective of the catalyst type used. the Linde spiral-wound reactor).. In the physical solvents the carbon dioxide dissolves without forming a chemical compound. and this allows recovery simply by flashing. 2.1. often in steps. often river water. to around atmospheric pressure.

methyldiethanolamine together with an activator. 183 allow a higher loading of the solvent. Primary and secondary amines. as shown in the last two lines of Table 15 depends largely on process configuration and required final purity which may range from 50 to 1000 ppm in the purified gas. New activators named ACT-1 (UOP) [510. 499] a sterically hindered amine. and in the few cases where it was used it was followed by additional scrubbing with monoethanolamine (MEA). For this reason tertiary amines are commonly used today. 516. in some cases. 491] amine borate. 2. there are no losses of the active solvent components. 513] (British Gas) have been introduced. 509. so recovery installations are not required. inhibitors to limit or prevent corrosion processes. The high thermal efficiency of this two-stage adsorption process using lean and semi-lean solvent is achieved by recompression of the flash steam with an injector or a mechanical vapor compressor. Heat requirements for regeneration in CO2 removal systems [331. The first generation of single-train steam reforming ammonia plants used MEA and consumed about 5. A typical example of an efficient modern hot potash system is the Benfield LoHeat [514] system of UOP.8 GJ per tonne NH3. BASF’s aMDEA [517–523] process uses an aqueous solution of the tertiary amine methyldiethanolamine (MDEA) with a special amine activator. The hot potash systems. Over the years considerable progress has been achieved in improving the efficiency of the carbon dioxide removal systems. UOP has also developed a number of other process configurations [498. No corrosion inhibitors are necessary. in the Giammarco Vetrocoke process glycine (originally arsenic oxide) [500–503]. The potassium carbonate processes from the various licensors differ with respect to the activator. for example. which Table 15.. All hot potash systems need corrosion inhibitors the concentration of which must carefully to be monitored. Table 15 demonstrates the progress made in energy consumption. monoethanolamine (MEA) and diethanolamine (DEA) exhibit a high masstransfer rate for carbon dioxide but have a high energy demand for regeneration.Vol. have good solubility in the applied solvents. for example. The following activators are used: in Benfield [492–495] and Carsol [496. kJ/mol CO2 MEA (without Amine Guard) 209 MEA (with Amine Guard III) Benfield hot potash (1-stage)a BASF aMDEA process (1-stage)a Benfield LoHeat BASF aMDEA process (2-stage)a 116 88 73 28 – 35 28 – 30 a b Single-stage regeneration. 837]. 515. 509] sulfosolvan B. and the solvent character is more like a hybrid between a strong chemical and a purely physical solvent. in the Exxon Flexsorb HP process [498. On account of the relative weak binding forces. The energy consumption of the modern systems. which was about 14 % of the total energy consumption. differ in the type of activator used to increase the reaction rate between the CO2 and the solvent. in the Catacarb system [490. 3 Ammonia.g. Very suitable for the partial pressure range of CO2 in steam reforming plants (4 – 7 bar) are chemical solvents based on aqueous solutions of potassium carbonate or alkanolamines containing additional activators to enhance mass transfer and. Two-stage regeneration. special process configurations are required for partial oxidation gases to recover separately a pure CO2 fraction and an H2S-rich fraction suitable for sulfur disposal. 497] process ethanolamines. and unlike MEA no solvent degradation is observed. the Benfield process licensed by UOP. a substantial amount of carbon dioxide can be recovered simply by flashing to low pressure. Triethanolamine does not achieve the required final CO2 concentration. Production Processes As both sour gases. Amine Guard introduced by Union Carbide) [528. in the Carbosolvan process [505. The activators enhance mass transfer and thus influence not only the regeneration energy demand (circulation rate of the solvent) but also the equipment dimensions. The carbon dioxide binds much less strongly to MDEA than to MEA. The first progress was made by addition of corrosion inhibitors (e. for example. 528] Process Heat requirement. CO2 and H2S. 511] and LRS-10 [512. 559–562]. corrosion inhibitor and to some extent in the process configuration. and only a small amount has to be . Owing to the low vapor pressure of MDEA and the activator. There is also a trade-off between energy consumption and investment costs.

but they have a rather high capacity for adsorbing water. and. the Rectisol process (Linde and Lurgi) [490. 2. and not very volatile. 3 ery in the regeneration stage is only partially possible (only pure CO2 can be obtained along with a CO2 fraction more or less rich in H2S) two principal plant flowsheets are possible.2 – 0. nontoxic.5 vol % CO and 0. 871] a theoretical analysis is given in [487]. which in this case has to operate over dirty shift catalyst (see Section 6. is positioned upstream of the shift conversion.1-dioxide þ diisopropanol) [504. a task difficult to fulfil with the other physical solvents mentioned. noncorrosive. These compounds and any water present have to be removed down to a very low ppm level. mainly H2S along with a minor quantity of COS. probably the most important in this connection. These solvents are stable. 518]polyethylene glycol methyl isopropyl ether. but at higher values physical solvents become increasingly preferable. In the lower half of this partial pressure range chemical solvents based on tertiary amines (e. The Selexol process (UOP) [490. This concept reduces the effort required to receive a highly concentrated H2S fraction suitable for further processing in a Claus plant or a sulfuric acid plant.1.005 – 0. 528. the typical synthesis gas still contains 0. Extensive surveys and additional literature of the CO2 removal processes are found in [489. the sour gases are removed after shift conversion. After bulk removal of the carbon oxides has been accomplished by shift reaction and CO2 removal.2 vol % CO2. 548–558. as all oxygen-containing substances are poisons for the ammonia synthesis catalyst [565]. It is actually the reverse reaction of steam reforming of methane: COþ3 H2 CH4 þH2 O DH ¼ 206 kJ=mol ð24Þ and CO2 þ4 H2 CH4 þ2 H2 O DH ¼ 165 kJ=mol ð25Þ The advantages of simplicity and low cost more than outweigh the disadvantages of hydrogen consumption and production of additional inerts in the make-up gas to the synthesis loop. In one. 854. Sepasolv MPE process. Examples of physical solvent processes are Selexol Process. with methanol as solvent operating at 15 to  40  C. Since the sour gases are both soluble in the solvents and a separate recov- Vol. depending mainly on feedstock and gasification pressure. which is usually achieved by chilling and operating at low temperatures. Before the solvent is recycled it has to be vacuum treated and/or air stripped to remove traces of carbon dioxide. When comparing the energy consumption of physical and chemical solvent based processes for a given application not only the heat for solvent regeneration but also the mechanical energy for solvent circulation has to be taken into account. no heat is necessary. Production Processes recovered by stripping. 529]. The reaction is carried out over a supported nickel catalyst at a pressure of 25 – 35 bar and a . Methanation. a first scrubbing stage. Lurgi Purisol Process (Nmethylpyrrolidone) [506–508]. 527. Physical solvent based processes can also be applied in steam reforming ammonia plants. Sulfinol process (tetrahydrothiophene-1. In the other arrangement. The Selexol Process for example operates at 5  C. Final Purification. Raw synthesis gas produced by partial oxidation has a carbon dioxide partial pressure between 10 and 30 bar.2) with the consequence that the H2S is diluted by a large amount of CO2. 543–547. the Sepasolv MPE process (BASF) [490. The process is very versatile: increasing the activator concentration shifts the character of the solvent more to the chemical side and vice versa. which removes the sulfur compounds. The presence of sulfur compounds. The second stage. The carbon dioxide is recovered simply by flashing. and the Fluor Solvent Process [539–542] polypropylene carbonate. removing pure CO2. methanol regeneration in the Rectisol process can be tailored to achieve a H2S-rich fraction for downstream processing and pure CO2. and process configurations include two.g.and single-stage designs. In this case.184 Ammonia. Methanation is the simplest method to reduce the concentrations of the carbon oxides well below 10 ppm and is widely used in steam reforming plants. introduces some complications for CO2 removal from partial oxidation gases. For this reason the raw gas has to be dry. MDEA) might be suitable. the latter allowing old MEA units to be revamped [524–526] simply by swapping the solvent without changing the process equipment. is located downstream of the shift reactors. 853. too. 530–538] uses polyethylene glycol dimethyl ether.. 871].

In this case the shift conversion is carried out in two stages with a special sulfurtolerant shift catalyst followed by removal of hydrogen sulfide and carbon dioxide in an acid gas removal unit. preferably at higher pressure in an intermediate stage of synthesis gas compression. the normal copper – zinc – alumina catalyst is usually not applied. the intensely exothermic methanation reaction can reach temperatures exceeding 500  C very quickly [566]. This results in a carbon monoxide content of the gas after shift conversion in the range 3 – 5 vol %. If a breakthrough of carbon monoxide from the low-temperature shift or carbon dioxide from the absorption system occurs. as well as the inert gas content of the purified synthesis gas fed to the synthesis loop. 573] has been proposed for partially replacing methanation. Liquid nitrogen wash delivers a gas to the . It is energetically advantageous to add the purified synthesis gas at a point in the synthesis loop where it can flow directly to the synthesis converter (see Section 6. a clean up Ammonia. The Selectoxo process (Engelhard) reduces the hydrogen consumption of the methanation system. Liquid Nitrogen Wash [581–583]. Normally. The required catalyst volume is relatively small.2). Additionally the inert level in the synthesis loop is reduced through this unit because methane is completely and argon is partially removed from the make-up gas. Cryogenic Methods are usually used for final purification of partial oxidation gases. Methanation as final purification for the raw gas from partial oxidation was proposed by Topsøe [567]. but it is also environmentally undesirable because of copper-containing wastewater. for the partial oxidation processes. The methanol may be recycled to the steam reformer feed or recovered as product. 3 temperature of 250 – 350  C. Production Plants. The carbon dioxide formed by the Selectoxo reaction adds only slightly to the load on the downstream carbon dioxide absorption system. Production Processes 185 methanation unit must follow the methanolation section. 3. Section 1.1. which is surprising as the same risk exists in partial oxidation based methanol plants for the similarly composed methanol catalyst. a rectifier column with an integrated condenser and turbo-expander. As full conversion of the carbon oxides is not achieved. At 185  C methane and argon are washed out. Methanol is removed from the gas by water scrubbing. For this reason water and traces of carbon dioxide must be removed from the make-up gas downstream of methanation. the cooled raw gas is mixed with the stoichiometric quantity of air or oxygen needed to convert the carbon monoxide to carbon dioxide. A prominent example is the Braun Purifier process [382.Vol. only a high-temperature shift conversion is used. commonly employed in early plants. Not only does it have a high energy demand. After low-temperature shift conversion. Methanolation [572.1). This is accomplished by passing the make-up gas through molecular sieve adsorbers. The purifier is a cryogenic unit placed downstream of the methanator and its duty is to remove the nitrogen surplus introduced by the excess of air used in the secondary reformer of the Braun ammonia process (! Ammonia. has become obsolete and is now operated in only a few installations. 1 % CO2 breakthrough leads to an adiabatic temperature rise of 60  C. 2. Because of the potential danger of a sulfur break-through causing poisoning. For example. It converts the residual carbon oxides to methanol.4. Another advantage of the process is that it separates the front-end and the synthesis loop. Controls should be installed and other security measures taken to avoid these high temperatures because the catalyst may be damaged or the maximum allowable operating temperature of the pressure vessel wall exceeded. Copper liquor scrubbing for carbon monoxide removal. Selectoxo Process. permitting the H/N ratio in the synthesis loop to be set independent of the secondary reformer. 574–580].3. The mixture is then passed through a precious-metal catalyst at 40 – 135  C to accomplish this selective oxidation [568–571]. The purifier is a relatively simple unit composed of feed/effluent exchanger. The cooling energy is supplied by expansion of the raw gas over the turbo-expander (pressure loss about 2 bar) and expanding the removed waste gas to the pressure level of the reformer fuel. but may be also incorporated in steam reforming plants. Dryers.

This process can be used to replace the LT shift conversion. causing explosions [584. with about 50 ppm argon and less than 10 ppm of other impurities. Prior to about 1950 gas generation processes and shift conversion operated at essentially atmospheric pressure. Reciprocating compressors with as many as seven stages in linear arrangement with intermediate cooling were used. Since this technology has proven its reliability in rather large hydrogen plants for refineries it is now also used for worldscale ammonia plants. 552. 6. an air separation plant is installed in conjunction with liquid nitrogen wash for economy in operation.2. Along with the introduction of pressure gasification. e. In these machines a good dynamic balance can readily be achieved. In some instances gas engines were used as drivers. Traces of nitric oxide (NO) may react with olefinic hydrocarbons. carbon dioxide removal. Production Processes synthesis loop that is free of all impurities. considerable savings in compression energy are achieved in this way. Careful surveillance of the inlet gases is required. 2. Higher pressures were used in a few installations. the air separation and the nitrogen wash frequently are closely integrated with one another so that economies can be realized in the refrigeration system. 3 the excess nitrogen introduced with the process air fed to the secondary reformer. including inert gases and is also the means for adding some or all of the nitrogen required for synthesis. the Linde LAC process (page 99). The gas was first compressed to the level of the CO2 removal section (usually 25 bar) and afterwards to around 300 bar for final purification (at that time usually copper liquor scrubbing) and synthesis. In a special version the nitrogen can be added in the PSA unit itself to increase hydrogen recovery [593–596]. The regeneration of the loaded adsorbent is achieved by stepwise depressurization and by using the gas from this operation to flush other adsorbers at a different pressure level in the regeneration cycle. Huge flywheels were designed as the rotors of synchronous motors (ca. and expansion. cooling. Machines with a suction volume up to 15 000 m3 (STP) for the first stage were not uncommon. in Claude and Casale units. It flows to the top of a wash column. In some processes it may also remove Vol. higher . horizontally balanced compressors in which the cylinders are in parallel configuration on both sides of a common crankshaft became the preferred design. The hydrogen recovery may be as high as 90 % depending on the number of adsorbers in one line. which may be as high as 10. Pressure Swing Adsorption. methanation. The rapid technical progress in the hydrocarbon based technologies of steam reforming and partial oxidation made it possible to generate the synthesis gas at a pressure level sufficient for the CO2 removal operation. which was around 300 bar in the majority of the plants at that time. 585].. In modern plants. whereby the CO2 removal section was usually installed between the 3rd and 4th stages.g. e. for example.’’ The wash column temperature is about 190  C. and even the secondary reformer as well [331. Water and carbon dioxide in the inlet gas will freeze. 125 rpm) with two crankshafts on both sides connected over crossheads with the piston rod for the horizontally arranged stages. 586–589].186 Ammonia. As gasification proceeds with a considerable volume increase and feedstocks such as natural gas are usually already available under pressure at battery limits. Liquid nitrogen wash systems are in operation at pressures up to 8 MPa corresponding to the highest gasification pressures. Very high purity can be obtained. It uses molecular sieves as adsorbents in a series of vessels operated in a staggered cyclic mode changing between an adsorption phase and various stages of regeneration. The process scheme for the ammonia plant may consist of production of pure hydrogen followed by separate addition of pure nitrogen from an air separation unit [590–592]. Normally. the LCA Process of ICI (page 97). where it countercurrently contacts precooled synthesis gas from which most of the methane and hydrocarbons have been condensed. causing operating difficulties. The nitrogen is liquefied in a refrigeration cycle by compression.g. Compression Up to the mid-1960s reciprocating compressors were used to compress the synthesis gas to the level of the synthesis loop. All of the cold equipment is installed in an insulated ‘‘cold box.

Further information on reciprocating compressors is given in [598. and this limits the possible length such that a compressor shaft cannot accommodate more than eight or nine impellers. natural gas. A further advantage is that centrifugal compressors require only a fraction of the space needed for reciprocating compressors. When gas engine drivers (two-stroke type) were used instead of electric motors. W. Sometimes special rotary compressors. which even for plants with 1800 t/d is between 155 and 190 bar [329. One of the most important features of the energy integrated single-stream steam reforming ammonia plant pioneered by M. process air. Kellogg in 1963 was the use of centrifugal compressors for the compression duties of synthesis gas and recycle. From this time onwards application of centrifugal compressors became standard practice in most ammonia plants irrespective of the synthesis gas generation technology. 3 speeds are possible and also the use of asynchronous motors is possible. 30). for example. In practically all modern ammonia plants. 599. 603]. e..g.8 mm) at the outer circumference of a centrifugal compressor impeller and this imposes a limit on the minimum effective gas volume leaving the last impeller. 600. allows simpler piping connections and facilitates maintenance. 601. with improved manufacturing techniques. In a very few cases steam turbines with special speed reduction gears have been used. A pressure increase. Of course. Depending on synthesis configuration. 2. The low height of the arrangement has less severe requirements for foundations. so-called mole pumps were also used. 331. exces- Ammonia. and high reliability (low failure rate) [830]. The first single-train ammonia plants with a capacity of 550 – 600 t/d had to lower the synthesis pressure to 145 – 150 bar to meet the required minimum gas flow condition. The tensile strength of the steels normally used to manufacture the compressor impellers allow a maximum wheel tip speed of about 330 m/s. and refrigeration. In most cases the centrifugal compressors in ammonia plants are directly driven by steam turbines.Vol. although the centrifugal compressors are inherently less efficient than reciprocating units. the minimum gas flow from the last wheel is 350 m3 for synthesis gas with a molecular mass of about 9 and an efficiency of around 75 %. In smaller plants. As newer synthesis catalysts allow a pressure of 80 bar in the synthesis loop (ICI’s LCA Process. from 25 to 200 bar would require 18 – 20 impellers. The fundamental advantage of these machines are low investment (single machines even for very large capacities) and maintenance cost. Manufacturing capabilities limit the minimum possible passage width (today about 2. a compressor shaft must have sufficient rigidity to avoid excessive vibration. rendering the machine extremely ineffective. for today’s world-scale capacities of 1200 – 2000 t/d these technical limitations have no influence on the synthesis pressure. Production Processes 187 sive pressure losses would occur within the passage and in the diffusers between the impellers. In older plants which used a reciprocating compressor for the recycle.8 to 3. less frequent shutdowns for preventive maintenance. the shaft of the final casing also bears the impeller for the compression of the recycle gas. with compression ratios from 1.2. It is therefore necessary to arrange several compressor casings in series. the various compression services. This corresponds to a capacity of 400 t/d at 145 bar. For this reason the overall efficiency of a plant with steam-driven centrifugal compressors is superior. were apportioned among the crankshaft throws in such a manner that a single compressor can perform all compression duties [597]. Today. However. To overcome the pressure drop (5 – 20 bar) in the synthesis loop re-compression of the recycle gas is required. with the unique feature that compressor and electric driver were completely enclosed in a common high-pressure shell. This avoids the losses associated with generation and transmission of electric power. some designs applied a common crankshaft for the piston rods of the gas machine cylinders and compressor cylinders. 604]. Fig. and synthesis gas compression. which limits the pressure increase attainable by each impeller. In old . mixing of make-up gas and recycle can be performed inside the casing or outside (three or four-nozzle arrangement. a recycle cylinder was often mounted together with the other cylinders on the reciprocating frame. Kellogg’s KAAP) a centrifugal compressor could be used down to 220 t/d. 602. process air. Unless the total volumetric gas flow has a reasonable relationship to the passage width of the last impeller and the pressure ratio.

l) Elevation for seal oil head . The high pressures and the high rotational speeds involved do not allow mechanical contact shaft seals. Sealing of the rotating shaft against the atmosphere is an important and demanding task. c) Pressure side. the make-up gas was introduced into the high pressure recycle loop and acted as the driving fluid of an injector which compressed the recycle gas. an oil film between the shaft and a floating ring. Production Processes Vol. Today modern plant concepts for world-scale capacity plants tend to limit the number of compressor casings to two. capable of rotation. These flexible couplings prevent possible compressor damage resulting from slight misalignment and shaft displacement. while the remainder flows against the gas pressure into a small chamber from which. together with a small quantity of gas. b) Bearing. Centrifugal compressor for make-up and recycle gas compression of an ammonia plant (courtesy of Uhde) a) Air cooler. In this concept. 2. liquid-film shaft seals with cylindrical bushings (floating rings) are applied [605].188 Ammonia. The seal oil pressure in the floating ring cavity must always be slightly higher than the gas pressure within the casing which is provided by Figure 29. h) Lube oil. d) Ambient side. Liquid film shaft seal with cylindrical bushing for a high-pressure centrifugal compressor a) Shaft. f) Seal oil surge vessel. The floating ring is usually sealed to the compressor casing by O-rings. provides the actual sealing. i) Drain to gas – oil separator. e) Floating seal rings. Geared or metal diaphragm couplings are used to connect the shafts of the individual casings (two in Figure 28). d) Water cooler Casale plants. 3 Figure 28. Figure 29 is a schematic diagram of a liquid film shaft seal. b) Separator. c) Silencer. Figure 28 shows an example of the synthesis gas compressor of a large ammonia plant. Part of the oil returns to the reservoir. g) Seal oil. k) Drain to lube oil tank. it is withdrawn through a reduc- tion valve. Seal oil flows between both halves of the floating ring. Usually.

it is necessary to re-circulate gas through individual stages or through the whole machine. the seal ring is pressed tight against the seat by means of a spring and the differential gas pressure. Dry gas seals in combination with oil-lubricated bearings (dry/wet) have the advantage that a much smaller oil system is required and that Ammonia. filters and (in part) pumps in common. which must withstand high thrust forces. The minimum clearances necessary at the labyrinths and the impellers allow practically zero wear. such as process air in steam reforming plants and air. Other compression duties in the plants. Nitrogen is used as an inert fluid for the seal. when the shaft is not rotating. kickback control) is designed to prevent this condition. which means without loss of efficiency. and oxygen. bearing damage. It is likely that this concept can be extended to a final pressure of 120 bar with ammonia synthesis gas. Often. If the volumetric flows through the machine at start-up or during reduced load operation deviate too far from the design values. 609]. A point of discussion is sometimes the minimum load at which the compressor can run without kickback. Compressors with three or four stages are in operation. are less prone to wear. An interesting concept is dry (oil-less) gas seals for centrifugal compressors. An increased vibrational amplitude is often an early indication of mechanical faults. where several compressors for synthesis gas and refrigeration duty equipped with dry seals have been successfully placed in service. already in commercial service. Anti-surge control (minimum by-pass control. for example. are also performed by centrifugal compressors. for example. Since then they have been widely used in off-shore service [606–608]. For these reasons.Vol. seal oil supply is combined with the lubricating oil system. such as rotor imbalance. and nitrogen compression in partial oxidation plants. it is necessary to seal the compressor shaft towards the atmosphere only at suction pressure level. which eliminates an emission source. Production Processes 189 there is no contact between oil and gas. Otherwise the compressor can enter a state of pulsating flow. Usually a load of 75 % is possible.. During stops.g. a methanol synthesis compressor for 75 000 m3/h and a pressure of 75 bar. but so far not used in ammonia plants. are less prone to developing vibrations due to imbalance and require less maintenance. Development dates back to 1969 and the first commercial application was in a natural-gas compressor in 1973. or misalignment. Also for the ammonia . A new development. This is especially true for the thrust bearings. Any wear resulting in friction could lead instantly to severe damage. Compressor control is achieved basically by controlling the rotational speed of the driver. The driver (e. and a small amount from the suction side may go to the atmospheric side and is sent to the flare on account of its content of combustibles. called surge. As the labyrinth section on the pressure side is connected with the suction side through an equalizing line. the axial position of the rotor and the radial vibrational deflections are continuously monitored by sensors. The high rotational speeds and the relatively large masses of the compressor rotors place high demands on the performance of the bearings. is magnetic bearings [606. 2. which could cause damage. in modern plants often with the help of a distributed control system (DCS). and with special impeller design. 3 static height difference of the oil level in the elevated oil buffer vessel. Magnetic bearings promise a wider temperature range. a steam turbine) drives a common gear to which the individual compression stages are connected. 25 000 rpm or higher. occurrence of friction. with oil reservoir. Integrated geared centrifugal compressors developed by DEMAG and GHH are a new development which might become of interest for plants of smaller capacity operating at lower pressure. which is achieved at the radial interface of rotating and stationary rings. Only recently have they gained acceptance in the ammonia industry. A combination of magnetic bearings and dry seals (dry/dry) could totally eliminate the oil system. Each stage has a single impeller which runs with very high speed. During operation the seal is not completely tight. as well as to minimize the incidence and degree of uneconomical re-circulation. in addition to measuring bearing temperatures. In this way normally no oil should enter into the synthesis gas. the value may be lowered to 70 % but with a slight sacrifice of full-load efficiency. some of the seal gas flows back to the suction side to be re-compressed.

When the make-up gas contains water or carbon dioxide. With this arrangement. The scheme shown in Figure 30 C. Figure 30 shows the principal possibilities. a higher ammonia concentration exists at the inlet to the converter. Production Processes compression in the refrigeration section centrifugal compressors are normally in service. As failures and breakdowns of these large rotary machines could lead to long and expensive repairs and to a corresponding loss of production it is advisable to keep the essential spare parts. it can be fed directly to the synthesis converter (Fig. at equal condensing temperature. spare rotors. 30 A). advantage is taken of the fact that these materials are absorbed completely by condensing ammonia. for example. 629].3. Figure 30 B shows the simplest such configuration. These basic features together with the properties of the synthesis catalyst and mechanical restrictions govern the design of the ammonia synthesis converter and the layout of the synthesis loop. This represents the most favorable arrangement from a minimum energy point of view. Ammonia is separated from the unreacted gas by condensation. If the make-up gas is absolutely free of catalyst poisons. The exhaust may be used for steam production.. In modern plants the synthesis gas compressors. 2. This arrangement has the disadvantage that the ammonia concentration for condensation is reduced by dilution with the make-up gas. after molecular sieve dehydration or liquid nitrogen wash). are almost exclusively driven by a steam turbines. These are generally extraction turbines with a condensing section. Additional information is given in [618–628]. An additional drawback of this arrangement is that all the ammonia produced must be compressed with the recycle gas in the recycle compressor. In older steam turbines.190 Ammonia. 6. This requires that the condensation stage be located partially or wholly between the make-up gas supply point and the converter. ammonia is condensed by cooling and the recycle gas is referred to the recycle compressor. sometimes blade failures occurred. for example.3. ammonia compressor. It results in the lowest ammonia content at the entrance to the converter and the highest ammonia concentration for condensation. 45 – 55 bar) to provide. In some cases screw compressors have been used for this duty on account of their good efficiency and load flexibility. avoids this waste of energy. and blowers. Synthesis Loop Configurations A number of different configurations are possible for the synthesis loop. . Criteria for compressor selection and economic comparisons are discussed in [610–617. 3 synthesis gas and recycled to the converter. and for other drivers. for preheating duties.1. the process steam in steam reforming plants. The unconverted gas is supplemented with fresh Vol. but this is no longer a problem due to improved blade design and shroud bands. After the gas leaves the synthesis converter.g. such as water and carbon dioxide (for example. Steam is extracted at suitable pressure levels (e. in stock. boiler feed water pumps. The concentration of the inert gases (methane and argon) in the synthesis loop is controlled by withdrawing a small continuous purge gas stream. which requires relatively low temperatures for reasonable efficiency.g. or as combustion air in the primary reformer [630–634]. the frequently used ‘‘four-nozzle compressor’’. air compressor. which is of interest in plants where the ammonia product is split between direct users at the site and cold storage in changing ratios. 6. Gas turbines have also been used as drivers for compressors in ammonia plants. so that only partial conversion of the synthesis gas (25 – 35 %) can be attained on its passage through the catalyst. including recycle. investment and reliability. which are standard today. Ammonia Synthesis Under the conditions practical for an industrial process ammonia formation from hydrogen and nitrogen N2 þ3 H2 2 NH3 DH ¼ 92:44 kJ=mol is limited by the unfavorable position of the thermodynamic equilibrium. They can be classified according to the location of ammonia condensation and the point at which the make-up gas is introduced. Also. Evaluation criteria are energy consumption. e.

b) Ammonia recovery by chilling and condensation. Converter performance is determined by the reaction rate. it is possible to cool the recycle gas using cooling water or air immediately before admixing the make-up gas (i. D) Two stages of product condensation a) Ammonia converter with heat exchangers. When ammonia-containing recycle gas and carbon dioxide containing make-up gas mix together under certain conditions of concentration and temperature. molecular sieve drying of make-up gas has increasingly been applied in order to realize the energy-saving arrangement of the synthesis loop corresponding to Figure 30 A. 2. 31). c) Ammonia recovery by condensation at ambient temperature. Production Processes 191 Figure 30. The effect of these parameters is discussed briefly in the following.Vol.e. At these pressures. In this configuration. B) Product recovery after recycle compression. before diluting the recycle gas) and thereby to reduce the energy expenditure for refrigerated cooling. e) Recycle compressor recycle compression follows directly after condensing and separating the ammonia. Formation of Ammonia in the Converter The central part of the synthesis system is the converter. This results not only from the more favorable equilibrium situation for the reaction. which depends on the operating variables (cf. 3 Ammonia.. in which the conversion of synthesis gas to ammonia takes place. In industrial practice. 30D).3. Typical operating parameters for modern synthesis loops with different pressures are listed in Table 16. but there are also those that operate at more than 40 MPa (400 bar). 6. precipitation of solid ammonium carbamate can result. 32). Schematic flow diagrams of typical ammonia synthesis loops A) Synthesis loop for pure and dry make-up gas. Splitting the cooling step for ammonia condensation also offers advantages when the recycle gas is compressed together with the make-up gas. there are plants that operate at about 8 MPa (80 bar).2. In recent years. The usual range is 0 – 15 vol %. Today. For a secondary loop . Converter performance decreases with increasing inert gas content (Fig. ammonia formation increases (Fig. but also from the effect on the reaction rate itself. also as a retrofit in existing plants.3). C) Product recovery before recycle compression (four-nozzle compressor design). Section 4. This applies especially at synthesis pressures above about 25 MPa (250 bar). d) Synthesis gas compressor. plants are built mainly for synthesis pressures of 150 – 250 bar. With increasing pressure. a greater portion of the ammonia formed can be liquefied by cooling with cooling water or air (see Fig.

 C Relative catalyst volume 4. Performance for a four-bed quench converter as a function of operating pressure with space velocity (per hour) as parameter. mol % Outlet NH3 conc.. a level of 10 ppm in the make-up gas. Usually. The optimum conversion at high space velocity [SV ¼ m3 (STP) gas h1  m3 catalyst] lies close to an H2 /N2 ratio of 2 and approaches 3 at low space velocities.0 5 1 3. Section 5. the ratio is adjusted to 3. The reason is that equilibrium plays a greater role at low space velocities and has a maximum at a ratio of 3. In practice. catalyst particle size is 6 – 10 mm Figure 33. In contrast to the above-mentioned variables. Performance of a converter as a function of inlet inert gas (CH4 and Ar) content with space velocity (per hour) as parameter. Today. Ammonia conversion as a function of hydrogen/ nitrogen ratios in the inlet synthesis gas with space velocity (per hour) as parameter. corresponding to about 3 ppm in the converter inlet gas.3. is usually. the ammonia Figure 32.. except for small corrections [1] with regard to the behavior of real gases. bar 140 220 Inlet flow.1. Converter performance also diminishes (Fig. 34). Production Processes Vol. 30 MPa pressure. mol % NH3 separator temperature.8 19. with increasing space velocity.5). 33) with increasing oxygen content of the synthesis gas. inlet NH3 content is 3. Typical operating parameters for modern synthesis loops at 140 and 220 bar (1000 t/d NH3) [329. Nm3/h 500 000 407 000 Inlet NH3 conc.1 8. 2.1 17. 226] Parameters Inlet pressure. 3 Figure 31. it can be 30 % or more (see Section 6. 9. the dependence of the converter performance on the H2 /N2 ratio shows a true maximum (Fig. space velocities vary from about 12 000 h1 at about 15 MPa (150 bar) to about 35 000 h1 at about 80 MPa (800 bar). Performance of a converter as a function of oxygen content (all oxygen-containing impurities) in the inlet synthesis gas Table 16.192 Ammonia.0 5 0.5 %.9 12. Usually. mol % Inlet inert conc.5). not exceeded (cf. conversions near equilibrium are attained.7 MPa pressure [832] ..6 Figure 34. p. because in most plants. 10 % inerts in the inlet synthesis gas based on purge gas.

Today the objective is to optimize the heat recovery (at the highest possible level) and to minimize the investment for the total synthesis loop. Achieving maximum ammonia production requires operating in the neighborhood of this ‘‘blow out’’ point. Additional equations describe the behavior of the separate feed – effluent heat exchanger system [638–642]. a still higher ammonia production rate is achieved. then Figure 35 shows that the converter temperature – composition profile should follow curve (a). a suitable mathematical model is required. This occurs when the heat of reaction is no longer sufficient to provide the temperatures necessary for operation of the feed – effluent heat exchanger. even with careful control. 34). in turn requiring very careful control [635–637]. The first models the concentration – position relationship for transformation of the reactants to products. and the vessel internals. see [638–642. then it is advisable to oversize the converter feed – effluent heat exchanger system to attain a higher degree of control stability. This raises the question of the definition of optimum. To maintain maximum reaction rate. If the objective in design or operation were optimizing catalyst utilization. From Figure 35 it is apparent that there is a definite temperature at which the rate of reaction reaches a maximum for any given ammonia concentration. The second handles the temperature – position behavior of the reacting synthesis gas. Two differential equations describe mathematically the steady-state behavior of the reactor Ammonia. the temperature must decrease as ammonia concentration increases. 55. 656]. 3 concentration in the effluent synthesis gas from a given converter does indeed go down (Figs. Section 4. 2. the reaction kinetic equation (cf. In the early days with more strict material and fabrication-related limitations the converters were usually designed for minimum high-pressure volume. Thus. It is also obvious that in reality this ‘‘ideal’’ temperature – concentration profile cannot be achieved. and for some of them optimum values have to be found.3). this characteristic can be used to maintain ammonia production rate when the synthesis catalyst ages and its activity declines. The reaction temperature profile is of particular importance because the reaction rate responds vigorously to temperature changes. However. a synthesis gas with about 3 % ammonia concentration entering the converter cannot be heated to the ‘‘ideal’’ temperature by heat exchange because the very high temperature required does not exist . The heat exchanger then fails to heat the cold converter feed gas to the required reaction ‘‘ignition’’ temperature.Vol. the catalyst. and pressure drop. To calculate the parameters for the design. which corresponds to maximum reaction rate at all points. i. For example. The design of an ammonia converter is a demanding engineering and chemical engineering task. Converter Design. Production Processes 193 section of a converter. 649]. other parameters have to be considered. the operating point normally chosen means that the increase in gas flow rate more than compensates for the reduced ammonia concentration. The line for zero reaction rate corresponds to the temperature – concentration dependence of the chemical equilibrium. too. General information on converter calculations are given in [52. Increasing converter flow rate and declining synthesis catalyst activity can reach a point.e. Figure 35 plots lines of constant reaction rate illustrating its dependence on temperature and ammonia concentration in the reacting synthesis gas. 641–643]. For example. Computer programs and applications can be found in [644–647]. gas compositions. The individual effects of the operational parameters are evaluated in [1. Plant operation often takes advantage of these phenomena. Models for multibed quench converters are described in [648–655]. Tubular reactors are treated in [657–664].. The form of the latter is characteristic of the type of converter. temperature profiles. including dimensions and number of catalyst beds. and this meant maximum use of the catalyst. where the reaction ‘‘blows out’’ and production ceases. For a discussion of modeling of different converter types. Design of ammonia synthesis reactors is not just the calculation of the required catalyst volume. 648. If the synthesis converter is to be operated in this region. The temperature profile depends not only on the rate of reaction heat evolution but also on the method and nature of the system for removing heat from the catalyst bed or beds. Curve (a) represents the temperature – concentration locus of maximum reaction rates. 31– 32.

Commercial Ammonia Converters. 2. The cooling medium is mostly the reactor feed gas. The different cooling methods can be combined in the same converter.4). 665].1. Today. In the days when converters were designed to operate at very high pressures and temperatures and before the advent of improved construction materials.e. 3 tion profile was often compared to the ‘‘ideal’’ for optimum usage of high-pressure vessel and catalyst volumes [656. Often. it is possible to minimize the required catalyst volume by cooling the reacting synthesis gas such that. Nitrogen reaction rate v in m3 NH3 /(m3 catalyst  s) as a function of temperature and ammonia concentration at 20 MPa pressure and 11 vol % inerts in the inlet synthesis gas a) Locus of temperatures resulting in maximum reaction rate at a given ammonia concentration in the converter system. This shields the outer shell from the high-temperature ‘‘basket’’. The catalyst volume is divided into several beds in which the reaction proceeds adiabatically. Production Processes Vol. permitting use of comparatively low-alloy chromium – molybdenum steels for its construction. Principal Reactor Configurations. part of the converter feed – effluent heatexchange system surface is placed within the converter pressure shell. By this means. the temperature follows curve (a). up to about 530  C. almost all converters consist of an outer pressure vessel containing a separate inner vessel housing the catalyst and other internals. To maximize converter output and plant capacity to achieve the most favorable overall manufacturing cost. the first portion of the catalyst must initially operate adiabatically. high temperature. Between the individual catalyst beds heat is removed by injection of colder synthesis gas (quench converters) or by indirect cooling with synthesis gas or via boiler feed water heating or raising steam (indirectly cooled multibed converters). Consideration of the service life of the catalyst requires that this maximum initial temperature not exceed that recommended by the manufacturer. cross-flow or radial flow pattern. 2. the nozzle penetration through the pressure shell for the converter effluent gas is also maintained at relatively low temperature..194 Ammonia. i. To reach the ‘‘ideal’’ temperature. Relatively cool converter feed gas flows through the annular space between the outer pressure shell and the internal ‘‘basket’’. this latter feature is not always necessary. usually 530  C (cf. the converter design represented a real limitation on plant capacity. Figure 35. which can flow counteror cocurrently to the gas flow in the synthesis catalyst volume (tube-cooled converters). Internally cooled with cooling tubes running through the catalyst bed or with catalyst inside the tubes and the cooling medium on the shell side. For example. . such as gas distributors and heat exchangers. the state of the art in converter construction materials now allows design of exit nozzles for the maximum anticipated temperatures. Commercial converters can be classified into two main groups: 1. The severe conditions of high pressure. A converter temperature – concentra- The gas flow can have an axial. Section 5. and high hydrogen partial pressures place strict requirements on the construction materials and design for both groups. Following this initial adiabatic temperature rise. it was necessary to optimize catalyst utilization. as ammonia formation progresses.

The mixture is heated to about 200  C in an internal exchanger located beneath the catalyst bed. 2. The reaction begins almost adiabatically in the catalyst bed. d) Main gas inlet. Tube-Cooled Converters. Fig. f) Temperature control gas (cold-shot) inlet. 488]. With these tubes. that cooling predominates and the temperature of the reacting gas begins to fall. Part of the feed gas to this unit enters the converter at the top and flows down through the annular space between the pressure shell and the basket. To remove the heat evolved in the synthesis reaction. Other tube-cooled converters with countercurrent flow are the Mont Cenis reactor [666–669]. 665. 36 A). As the reacting gas temperature rises. converters have been designed in which cooling tubes run through the catalyst bed. Typical of such converters is the countercurrent design of the Tennessee Valley Authority (TVA) [635. the heat is transferred to the converter feed gas to heat it to the reaction ignition temperature or to an external cooling medium. Production Processes 195 Figure 36.Vol. 36 B). and the older Fauser design [484]. c) Cooling tubes. 3 Ammonia. Cold converter feed gas can be admitted at a point within the internal heat exchanger to control both the total system and reaction temperature profiles through bypassing. 35) References [670] and [671] review some literature on ammonia converters. When designed to utilize the heat of reaction for heating the converter feed gas. Countercurrent tube-cooled converter (TVA converter) [665] A) Converter layout. The known designs for such converters are suited only for small production capacities and therefore currently of limited interest. Casale has employed a similar converter design concept [685]. the Claude converter [484. e) Vessel wall cooling gas inlet. a) Catalyst. resulting in increasing heat removal (Fig. There it absorbs the heat released in the reaction and reaches the required reaction ignition temperature of about 400  C. the rate of reaction begins to decrease sufficiently. the temperature difference between the reacting gas and the cooling tubes increases. such converters have the further disadvantage that temperature control is sluggish and temperature oscillations dampen out very slowly. C) Ammonia concentration versus temperature (cf. g) Gas exit B) Gas temperature profile through the converter. the original Haber – Bosch reactors [666]. 662. The reaction temperature at first somewhat exceeds that for maximum reaction rate but eventually falls below curve (a). a phenomenon called ‘‘hunting’’. Figure 36 C shows the converter temperature – concentration profile. 674–676. if at all. As the reacting gas reaches the bottom of the catalyst bed. These converters were . The main gas flow enters the converter at the bottom and joins the shell cooling gas. b) Heat exchanger. 682–684]. because of high ammonia concentration. The gas then enters the cooling tubes that run through the catalyst bed (Fig.

the point where maximum reaction rate – therefore maximum rate of heat evolution – is taking place. 2. 3 The Nitrogen Engineering Corporation (NEC) converter applies cocurrent flow by means of bayonet tubes [665. 38 C). a) Catalyst. c) Cooling tubes. Fig. 35) . and heat exchanger.196 Ammonia. 674. The plates are radially immersed in the axial – radial catalyst bed to remove the reaction heat while it is formed. Figure 38 A shows the general arrangement of the converter. b) Heat exchanger. maximum cooling performance – at the catalyst bed inlet. 676–683]. Figure 39 [879] shows the temperature profile of this pseudo-isothermal reactor. An interesting rebirth of the countercurrent principle is the new ICI tube cooled converter used in the LCA process (Fig. catalyst bed. The intent is to obtain closer approach to curve (a) (cf. Chemico. e) Temperature control gas (cold-shot) inlet. C) Ammonia concentration versus temperature (cf. c) Catalyst. Ammonia Casale developed a new converter concept which uses no tubes but arranged cooling plates. all used in relatively small plants and are now obsolete. the temperature profile of the system. d) Gas inlet. This design places maximum heat-exchange temperature difference – therefore. The profile follows the line of the maximum reaction rate to obtain the highest possible conversion per pass from a given catalyst volume. Figure 38 B. 37) [873]. continued to apply such converters with only slight changes [685]. ICI tube-cooled ammonia converter a) Top of catalyst bed. f) Gas exit B) Gas temperature profile through the converter. Cocurrent-flow tube-cooled converter [665] A) Converter. Fig. Production Processes Figure 37. b) Cooling tubes. The use of plates allows a design without tubesheets and simplifies catalyst Figure 38. Vol. a derivative of NEC.

or be just defined by the location of cold gas injection tubes as for example in the ICI lozenge converter. Production Processes 197 Figure 39. Expected thermal profile of catalyst along the converter and comparison with plant data [879] loading and unloading and the use of small size high active catalyst. Therefore a higher catalyst volume is needed compared to an indirectly cooled multibed converter. the great majority of synthesis converters are designed with catalyst distributed in several beds. Today. In this type of converter only a fraction of the recycle gas enters the first catalyst layer at about 400  C. unconverted synthesis gas (cold shot) between the catalyst beds. 500  C (catalyst suppliers specify a maximum catalyst temperature of 530  C). 41). so that the total volume of the high-pressure vessel will remain about the same as that for the indirectly cooled variant [700]. and direct or indirect cooling is provided between the catalyst beds for cooling the reacting mixture from a temperature above to a value below the ‘‘ideal’’ (curve (a). the synthesis gas reacts adiabatically. Internals of a Casale isothermal converter (courtesy of Ammonia Casale) subsequent beds. Multibed Reactors with Direct Cooling (Quench Converters). the gas is ‘‘quenched’’ by injection of cooler (125 – 200  C) recycle gas. However. . 3 Ammonia. In quench converters cooling is effected by injection of cooler. The new Casale IAC ammonia converter is suited for very high capacities up to 4500 t/d for the the so-called mega-ammonia plants presently in discussion. The same is done in Figure 40.Vol. In each bed. A disadvantage is that not all of the recycle gas passes over the entire catalyst volume so that considerable ammonia formation occurs at higher ammonia concentration and therefore at lower reaction rate. Before it enters the next catalyst bed. In this way the reaction profile describes a zig-zag path around the maximum reaction rate line. 40). no extra space is required for interbed heat exchangers. 2. A schematic drawing of a quench converter together with its temperature/ location and temperature/ammonia concentration profiles is presented in Figure 41. within one or more reactor vessels. Fig. The first commercial use of a converter of this type is operating successfully in a 1050 stpd (953 mtpd) plant in Trinidad [855]. The catalyst beds may be separated by grids designed as mixing devices for main gas flow and cold shot. In a recent Casale company brochure the plate arrangement is shown taking a methanol converter as an example (Fig. The catalyst volume of the bed is chosen so that the gas leaves it at ca.

and others. b) Catalyst bed. For example. e) Interchanger. b) Heat exchanger. An interesting variant in this group is the ICI lozenge converter [213. c) Quench gas inlets. Fig. d) Quench. For this reason it is justifiable to classify this converter as a multibed type. This design (Fig. 701–703] (Figure 42). 682]. Kellogg three. 35) As the quench concept was well suited to large capacity converters it had a triumphant success in the early generation of large single-train ammonia plants constructed in the 1960s and 1970s. W. 666. Casale [671]. d) Gas inlet. Grand Paroisse [670]. Descriptions of earlier designs of Kellogg. Kellogg alone has installed more than 100 of its quench converters. Kellogg four-bed vertical quench converter a) Gas inlet. is designed for disassembly. 3 Figure 41. In this design. Though being increasingly replaced by the indirect-cooling concept by revamp or substitution they are still extensively used. attached to the top head. Multibed converter with quench cooling [833] A) Converter. the catalyst ‘‘basket’’ is not easily removable from the pressure vessel. and Uhde can be found in [671–673. 2. c) Basket. 701]. Other designs were used by BASF [671]. The distributors consist of banks Figure 42. 43) has a single catalyst bed that is divided into several zones (usually four) by quench gas distributors. through which colder recycle gas is injected evenly across the whole cross section of the catalyst bed. C) Ammonia concentration versus temperature (cf. Uhde [671]. W.or four-bed converter [671.198 Ammonia. 671. The converter feed – effluent exchanger. BASF. g) Bypass . Chemico. The catalyst can be changed by draining it at the bottom of the converter through ‘‘downcomers’’ that connect all catalyst beds with one another. 685. e) Gas exit B) Gas temperature profile through the converter. M. Mechanical simplicity and very good temperature control contributed to the widespread acceptance. Production Processes Vol. f) Gas outlet. The most important example is the M. ICI [671]. a) Catalyst.

The spargers are in a void space within horizontal mesh-covered structures.Vol. The first radial flow converter introduced commercially and then widely used was the Topsøe S 100 converter [666. and with this concept it is possible to design converters for very large capacities without excessive diameters and with low pressure drop. 705]. it enters the second bed and passes through it in the inward direction. 714–719]. After the effluent from the first bed has been quenched with cooler recycle gas. The major part of the gas enters the vessel at the top and flows down as shell cooling gas. 3 Figure 43.5 – 3 mm. with down-flow in the upper half and up-flow in the lower half of the catalyst bed. which is traversed from the inside to the outside. Production Processes 199 freely past them during loading and unloading. To compensate for the increasing pressure drop conventional axial flow converters have to use relatively large catalyst particles. 671. ICI lozenge converter a) Quench gas distributors. suggested for very large capacities. even with small catalyst particle size. Radial flow has been also applied in tube-cooled converters [712]. Radial flow quench converters have also been ¨ sterreichische used by Chemoproject [721]. d) Tube for thermocouples of transverse sparge pipes which deliver gas at regular intervals along their length. A special version of this reactor concept is the opposed flow design [704. In this configuration the converted gas is collected and withdrawn from the middle of the catalyst bed. The uninterrupted catalyst bed is maintained in the opposed-flow converter. 701. which have the disadvantage of lower activity compared to smaller particles mainly on account of diffusion restriction. . whose cross section is lozenge shaped so that the catalyst particles can flow Ammonia. A design similar to that of ICI with direct injection of the quench gas into the single catalyst bed has been proposed by Chemico [706]. Converters with axial flow face a general problem: with increasing capacity the depth of the catalyst beds must be increased because for technical and economic reasons it is not possible to increase the bed diameter. O Stickstoffwerke [722]. above a certain limit. Figure 44 shows a schematic of the converter [329]. It then passes through the feed – effluent heat exchanger and flows upwards through a central pipe to the first catalyst bed. c) Catalyst discharge nozzle. 2. Radial gas flow in the converter avoids this dilemma. which has two catalyst layers with a catalyst particle size of 1. The advantages of radial flow are discussed in [708–711]. b) Heat exchanger. and Lummus [723]. The cold gas enters through the bottom of the vessel and is mixed with the inlet gas to the first bed for temperature control. and thus the pressure vessel diameter.

In the Casale concept there is no need for a dead catalyst zone as the annular catalyst bed is left open at the top to permit a portion of the gas to flow axially through the catalyst. especially for large capacities. 716. As shown in Figure 45 this is achieved by leaving the upper part of the catalyst cartridge at outlet side unperforated so that gas entering from the top is forced to undergo partially axial flow. Figure 46 shows a schematic of the principle together with temperature/location and temperature/ammonia concentration profile. c) First catalyst chamber. Converters with strictly radial gas flow require mechanical sealing of the top of each catalyst bed and dead catalyst volume with little or no flow to avoid bypassing of the catalyst. 715. 3 Figure 45. g) Second catalyst chamber. Multibed Converters with Indirect Cooling. The remainder of the gas flows radially through the bulk of the catalyst bed. Haldor Topsøe S100 converter a) Outer internal lid. As the cartridge is equipped with wheels it can be moved in and out on tracks. The heat exchanger may be installed together with the catalyst beds inside one pressure shell. 695. Production Processes Vol. 725. n) Refractory cement Axial – radial flow pattern was introduced by Ammonia Casale. j) Catalyst support plate 2. e) Perforated center tube. 726. W. i) Outer annular space. and also in revamps an increasing number of quench converters are modified to the indirect cooling mode.200 Ammonia. This approach is especially suitable when using the reaction heat for raising high-pressure steam. The catalyst beds are arranged side by side in a removable cartridge which can be removed for catalyst loading and unloading through a full-bore closure of the horizontal pressure shell. The temperature difference between the top and the bottom requires special design measures to prevent uneven circumferential warming of the pressure shell and to avoid bending. k) Heat exchanger. Crossflow was chosen as a different approach by M. f) Catalyst support plate 1. is to accommodate the individual catalyst beds in separate vessels and use separate heat exchangers. In converters of this type cooling between the individual beds is effected by indirect heat exchange with a cooling medium. b) Inner internal lid. The gas flows vertically from the top to the bottom. b) Perforated wall Figure 44. 2. l) Refractory fiber. m) Pressure shell. but an attractive alternative. which may be cooler synthesis gas and/or boiler feed water heating and steam raising. 835]. Ammonia Casale axial – radial flow pattern a) Unperforated wall. d) Inner annular space. thus needing no crane. The indirect cooling principle is applied today in most large new ammonia plants. h) Transfer tube. Kellogg in their horizontal quench converter to obtain low pressure drop even with small catalyst particles [670. .

670. Two versions are shown in Figure 47. 671. . Multibed converter with indirect cooling A) Converter. Casale [738–743] has also successfully commercialized converters based on the axial – radial flow concept with indirect cooling. designed for indirect cooling. In the well-known Uhde – Chemie Linz converter with three catalyst beds – described in various versions [656. 670. Production Processes 201 Figure 46. tube coils between catalyst beds transfer the reaction heat to a closed hot water cycle under pressure. f) Gas exit B) Gas temperature profile through the converter. For trimming purposes a quench is foreseen. 708. Feed gas enters at the top. with and without a lower internal heat exchanger. C) Ammonia concentration versus temperature (cf. 671. a) Catalyst. After passing the centrally installed interbed exchanger on the tube side. In the converter without a lower exchanger the feed gas enters at the bottom and flows as pressure wall cooling gas to the top of the converter. the Fauser – Montecatini reactor [666. Further development of the radial flow concept used in the quench converter Topsøe Series 100 has led to the successful launch of the Topsøe Series 200 converter [477. The gas passes downwards through the catalyst beds and the tube side of the interbed exchangers and the lower heat exchanger to leave the reactor vessel. A ‘‘cold shot’’ ahead of the first catalyst bed is installed for temperature adjustment. c) Cooling section. Fig. 732–736]. the gas is mixed with cold gas for temperature adjustment and passes through the first catalyst bed radially from the outside to the inside. The Topsøe Series 300 converter contains three catalyst beds and two central interbed exchangers in a single pressure shell. 728–730].8 t of steam per tonne of ammonia at about 45 bar (ca. The exit gas flows through the shell side of the interbed exchanger before it enters the second bed.Vol. 701] – the indirect cooling is provided by converter feed gas. 686–689. and then via the center pipe and interbed exchangers to the top of the first catalyst bed. b) Heat exchanger. passes down the annulus between basket and shell to cool the pressure wall. e) Temperature control gas (cold-shot) inlet. operating by natural draft. 250  C). 682. 691. for example. flows through the shell side of the lower feed – effluent heat exchanger. which is crossed in the same direction as the first one. 35) Converters with indirect cooling have been known since the early days of ammonia production. d) Gas inlet. In this converter. 690. 3 Ammonia. The hot water releases the absorbed heat in an external steam boiler generating about 0. 2.

h) Cold bypass pipe Kellogg has re-engineered its horizontal crossflow quench converter for indirect cooling [670. 744–747]. c) 1st Catalyst bed. To withstand the high outlet temperature level (450 – 500  C) needed for the high-pressure boilers. Chapter 1). A horizontal design with indirect cooling is also proposed in [754]. The gas flow is axial and the mechanical design rather simple. 753]. b) Interbed heat exchanger. Production Processes Vol. The reactor contains two catalyst beds. and an inlet – outlet heat exchanger is located between first and second bed. which is possible with modern steels in compliance with the Nelson diagram (see ! Ammonia. d) Annulus around catalyst bed. . In a later version three catalyst vessels [747–751] with boilers after the second and the third were used. b) Interbed heat exchanger. d) Bed 1. Topsøe Series 200 converter a) Pressure shell. the pressure vessel wall of the C. e) 2nd Catalyst bed. c) Bypass. 3. Braun has devised a good solution by direct coupling the boilers and the exchanger to the converter. which discharges through a second external high-pressure boiler. in which the pressure shell is kept below 250  C by means of insulation or by flushing with cooler gas. Reactor feed gas passing between cartridge and shell is used to keep the pressure wall cool. Production Plants. 696. Then a waste-heat boiler generating high-pressure steam cools the gas before it enters the second vessel containing the third bed. Uhde has used three catalyst beds for capacities up to 2300 t/d (Fig. e) Bed 2. F. In the C. 3 Figure 48. and the second catalyst vessel was followed by a waste-heat boiler for high pressure steam. 695. Figure 49 shows the two-bed version of the C. 698. F. C. The first two are accommodated in a single pressure vessel together with an inlet – outlet exchanger. Braun ammonia synthesis concept [697. The gas flow is in radial mode in all three catalyst beds. Contrary to most converter designs. 48) As in the quench version the pressure shell has a full-bore closure to remove the catalyst cartridge for loading and unloading. Kellogg horizontal intercooled ammonia converter a) Inlet. (Fig. The feed – effluent heat exchanger was located between the first and second reactor vessels. Braun converter. a special design is employed to keep the outlet nozzle cool. separate vessels were used for the two catalyst beds in the original version. f) Outlet Figure 47. 50).202 Ammonia. Braun reactors is at 400  C. 752. F. This basic concept was already introduced in the heyday of the quench converters and prior to the first energy crisis. f) Lower heat exchanger. F. with the second one split into two parallel sections. 2. g) Cold bypass. A cold shot is installed for adjusting the inlet temperature of the first catalyst bed.

394] a special converter design. Four radial flow beds are accommodated in a single pressure shell with intermediate heat exchangers after the first. 2. From the effluent about 85 % of the ammonia produced is removed from the gas before it is compressed in the high presure casing to 210 bar to enter the well-known Uhde two-vesselthree-bed combination as described above. 3. The syngas with 110 bar from the lowpressure casing of the compressor is fed to a three-bed. Saudi Arabia (Safco IV). Topsøe has now introduced a hot-wall converter with only one catalyst bed and no internal heat-exchange equipment. but with radial flow. similar to C. Kellogg has developed for its ruthenium catalyst based KAAP ammonia process [331. This is so far world-wide the largest capacity in a single synthesis (see also ! Ammonia.Vol. Braun converters with interbed heat exchanger and waste-heat boiler a) Gas inlet. This Topsøe Series 50 converter. Three of these converters can be combined with an external heat exchanger and two high-pressure boilers to give an arrangement as described for Braun. Uhdes standard synloop configuration a) Ammonia converter. b) Feed – first bed effluent exchanger. The first plant based on this concept with a capacity of 3300 t/d will come on stream 2006 in Figure 50. e) Line to second bed. h) Steam drum. For revamps Kellogg has also proposed a twobed version completely loaded with ruthenium catalyst to be placed downstream of a conventional converter [395]. c) Refrigeration Al-Jubail. second and third bed. intercooled. Figure 51 shows the Uhde dual pressure concept. c) Bypass for temperature control.F. Production Plants. The first bed is loaded with conventional iron catalyst. suited for very large capacities. Production Processes 203 Figure 49. C. can also be combined with the Series 200 reactor and two external high-pressure boilers to attain the configuration as described for Uhde (Topsøe Series 250). b) Syngas compressor. once-through converter which can produce a third of the total ammonia yield. Braun. Section 1. i) Steam outlet. f) Second bed.4). the following ones with the new ruthenium catalyst. k) Gas outlet A new development is the Uhde dual pressure process [856–861]. d) First bed. F. 3 Ammonia. g) waste-heat boiler (Borsig). Figure 52 is a simplified sketch of the synthesis loop of the KAAP Figure 53 shows the internals of the KAAP converter [864]. .

720. 400  C) . requiring greater total catalyst volume and appropriate changes in the catalyst bed dimensions. e) HP casing. b) Second ammnia converter. f) Oncethrough ammonia converter Optimizing the Temperature Profile and Bed Dimensions in Multibed Converters.22 kJ/mol at STP. which corresponds to 2. the volume of catalyst required in the individual beds increases. 727. 724. Early converters. Utilization of this heat at the highest possible temperature for generating high-pressure steam is a major contribution to the high total energy efficiency of modern ammonia plants [755]. 665.72 GJ per tonne NH3. Waste-Heat Utilization and Cooling The reaction heat of ammonia synthesis is 46. 2. The literature has frequently treated the problem of optimizing both the distribution of catalyst volume between a given number of beds and the bed inlet temperatures [638. equipped with a lower heat exchanger for raising the inlet temperature for the (first) catalyst bed to the ignition temperature (ca. see also page 65. b) Purge gas recovery unit. received the converter feed at about ambient temperature and therefore had outlet . Reference [737] examines optimizing the temperature profile in a given four-bed quench converter. With closer approach to equilibrium.3. operating at about 300 bar. d) LP casing. 640.204 Ammonia. Kellogg advanced ammonia process (KAAP) a) Compressor. c) Purge gas recovery unit. For additional literature on this important issue in converter layout and design. Uhde dual pressure ammonia synthesis concept a) First ammonia converter. c) Refrigeration 6.3. Figure 52. Production Processes Vol. 731]. 3 Figure 51.

2 KAAP catalyst. Appropriate designs of waste-heat boilers are described in ! Ammonia. 3. Advanced ammonia concepts produce as much as 1. as optimum energy efficiency of the whole ammonia plant requires maximum high-pressure steam generation. Initially there was practically no heat recovery. 15. This can be accomplished [732. As for any type of converter the outlet temperature rises with increasing inlet temperature (DT is determined by the degree of conversion). which means that the gas can be cooled in the boiler to ca. 4 KAAP catalyst temperatures of ca. 2. part of the heat must be recovered before the reaction is completed in the reactor system. . downstream of the above-mentioned heat recovery. In some instances. In practice this corresponds to moving the lower heat exchanger (which in multibed converters exchanges feed to the first catalyst bed against effluent from the last bed) partially or completely to a position outside of the converter and downstream of the waste-heat recovery installation. but the low temperature level allowed only boiler feed water heating and generation of low-pressure steam (ca. 755. 3 Figure 53. 733. The trend followed in newer plants is to increase conversion per pass with the result of higher ammonia outlet concentrations and lower outlet temperatures from the last bed. the remaining recoverable heat is used for boiler feed water heating. F. Section 1. However.3. water circulation was in- Ammonia.5 t of high-pressure steam per tonne of ammonia. formerly 100 bar. d) Bed no. Subsequently plants were modified to use this heat to some extent. KAAP four bed ammonia converter a) Bed no.5  C per mol % of ammonia formed). Production Plants. 320  C) is generated after the second catalyst bed. Braun arrangement. 756] by using three catalyst beds in separate pressure vessels with boilers after the second and the third vessel and an inlet – outlet heat exchanger for the first catalyst bed. b) Bed no. 350  C . Figure 54 is a temperature – enthalpy diagram for a converter system corresponding to the original C. High-pressure steam (113 bar. which correspond roughly to 90 % of the standard reaction enthalpy. has now been raised to 125 bar. In this way the waste-heat downstream of the synthesis converter in modern plants is available in the temperature range around 480 to 290  C. 250  C (ca. in further developments an additional heat exchanger for converter feed versus the converted gas was installed. c) Bed no. In this way the temperature level at which heat could be recovered was increased.Vol. ultimately to the point where the inlet temperature to waste-heat recovery is equal to the outlet temperature of the last catalyst bed. 20 bar). 3 KAAP catalyst. Production Processes 205 stalled to use this heat in other plants or production steps. and nearly the total heat content of the gas down to ambient temperature and thus the reaction heat was transferred to cooling water. 1 magnetite catalyst. The steam pressure.

h) Cooling in main feed effluent exchanger 6. see also Figure 30). Temperature versus enthalpy diagram for a twobed system with steam generation a) Heating in main feed effluent exchanger. All ammonia vapors removed from flash gases and from purge gas by water scrubbing can be recovered as pure liquid product by distillation if there is no direct use for the aqueous ammonia. Although ammonia condensation was already used in HABER’s lab-scale ammonia plant and in early pilot plants of BOSCH.5 mol % by absorption in dilute aqueous ammonia. the first commercial units of BASF used ammonia absorption in water to remove the product from the cool synthesis loop gas. In the early 1920s LUIGI CASALE successfully used condensation for his first plant. The amount of ammonia vaporized (and consequent- Vol. 792] has proposed removing the ammonia from the loop gas at ambient temperature down to 0. Recovery of ammonia by water scrubbing offers the advantage of achieving a very low residual ammonia content. recirculation compression. d) Cooling in feed – first bed effluent exchanger. which operate at moderate pressures. The extent to which the ammonia concentration in the gas can deviate from that expected . 780] did not find widespread application. The liquid ammonia of the high-pressure separator is flashed to about 20 bar. preferably after removal of ammonia vapor to avoid NOx formation in the combustion furnace. The ammonia from the let-down vessel may be sent directly to downstream users or flashed further to atmospheric pressure for storage in a cold tank. Refrigeration down to  25  C is used. 772. because various technical problems were encountered with refrigeration at that time.206 Ammonia. Arrangement and location of the ammonia separator(s). Snam Progetti [213. g) Temperature level of waste-heat boiler.4. This gas is normally used as a fuel. addition of make-up gas and extraction of purge gas are discussed in Section 6. f) Cooling by steam generation.3. Nevertheless the scrubbing route was again proposed for a synthesis loop to be operated under extremely low pressure (around 40 bar) [787]. The liquid ammonia product is separated from the gas. 791.3. b) Further heating in feed – first bed effluent exchanger. but the drawback is that the whole recycle gas has to be dried afterwards and in addition distillation of aqueous ammonia is necessary to yield liquid ammonia. Production Processes Figure 54. It was only in 1926 that ammonia condensation was introduced in the Haber – Bosch plants. In older high-pressure synthesis loops (> 450 bar) cooling by water and or air is sufficient to obtain the required low residual ammonia concentration in the gas. the cooling has to be supplemented by refrigeration. Water cooling was sufficient on account of the very high synthesis pressure. e) Temperature rise in second bed. with one or more temperature levels is generally used. At a loop pressure in the range 100 to 150 bar the quantity of reliquefied ammonia may be twice the ammonia product flow. which is recycled. 3 ly reliquefied by compression and water or air cooling) can be substantial. 764. c) Temperature rise in first bed. for which a mechanical ammonia refrigeration cycle. In modern plants. Absorption refrigeration with aqueous ammonia instead of a mechanical refrigeration system [757. Ammonia Recovery from the Ammonia Synthesis Loop In all commercial plants ammonia is recovered from the synthesis loop by cooling the synthesis gas to condense the ammonia under synthesis pressure.1. 778. 2. 770. whereby the majority of the dissolved gases are released in the let-down vessel. which with inclusion of the necessary temperature difference in the chiller requires ammonia evaporation at about atmospheric pressure.

With a higher inert gas content in the make-up gas this method is not applicable. 6. Table 4 is 1. Table 4 and ! Ammonia. 1. under 0. Therefore.3. This system has the advantage that nitrogen is also recovered. 300 bar). These include methane (from gas generation). for example. only a very small final purge stream is necessary and no recompression is needed. Moreover. For this reason other methods have been developed. Because they are inert.84 mol % at the total pressure of 20 bar. As this loop can operate at a very high inert level (40 % or more). in addition to removal as dissolved gases (flash gas).5 MPa (75 bar). inerts have also to be removed from the gas phase by withdrawing a small purge-gas stream from the loop. c) Plate-fin exchanger. d) Separator. 1. Introduction. they tend to concentrate in the synthesis loop and must be removed to maintain the loop material balance. A high inert gas level has various drawbacks. 795]. Introduction. Piping and equipment must correspondingly be increased in size. and the inert gas concentration in the synthesis loop make-up gas low enough.Vol. Simplified flow diagram of cryogenic hydrogen recovery unit a) Molecular sieve adsorbers. 1. Introduction. Figure 2 gives vapor – liquid equilibrium ratios for use in making precise calculations of the dissolved quantities of inerts. Table 5 gives the ammonia concentration in a 1/3 nitrogen/hydrogen mixture at 20 bar total pressure as 9. ! Ammonia. 3 for ideal behavior can be seen from ! Ammonia. h) NH3 refrigerant . but it is too expensive for use in modern plants and revamps. If the synthesis gas pressure is high. Molecular sieve adsorbers then eliminate moisture and traces of ammonia (Fig. and helium (from the natural gas). the fresh make-up gas supplied to the synthesis loop usually contains small quantities of inert gases. So.8 mol %. The dry. ! Ammonia. 1.167 bar. Table 5. Inert-Gas and Purge-Gas Management Apart from nitrogen and hydrogen. Production Processes 207 by reducing the hydrogen and nitrogen partial pressures. 1. Introduction.2 vol % [793]. there is an unfavorable effect on condensation of the ammonia product. corresponding to 5. 1. b) Heater. e) Ammonia-free purge gas. For example. Up to 75 % of the hydrogen from the first-loop purge stream can be recovered. 55). then dissolution in the product ammonia suffices to remove the inerts from the synthesis loop. Table 6 gives a rough approximation of the extent to which these inerts are dissolved. Ammonia is first removed from the purge gas by cooling or in a water wash operating at 7. At the same time expensive synthesis gas is also lost from the loop. There are several possibilities for reducing the losses associated with the purge gas. ! Ammonia. Hydrogen Recovery by Cryogenic Units [773]. In contrast. because the required partial pressure of the inert gas at equilibrium in the loop gas would become so high that a synthesis under moderate pressure would be virtually impossible. The gas recycle flow is increased by the amount of inert gas. A portion of the inert gases dissolves in the liquid produced in the ammonia separator. f) Fuel gas to reformer burners. for example. The most capital-intensive method consists of feeding the purge gas to a second synthesis loop operating at a slightly lower pressure [794. and the associated power consumption for recycle gas increases. determining the appropriate inert gas concentration requires a precise economic calculation. at 30 bar the ammonia vapor pressure according to ! Ammonia.5. ammonia-free purge gas from Figure 55. Because of the dilution. argon (from the process air). Introduction. It decreases the specific converter performance Ammonia. which lowers the ammonia yield. Introduction. 2. less ammonia can be condensed from the recycle synthesis gas by less expensive air or water cooling or higher temperature level refrigeration. g) Hydrogen product to syngas compressor.

The hydrogen-rich gas also flows into the same exchanger (in separate passages) where the vaporizing liquid and the hydrogen are warmed by cooling the entering purge gas. and number of separators determined by ammonia process). The remaining (nonpermeating) gases. After heating in a preheater. The gas stream enters the separator on the shell side. reducing the ammonia concentration to less than 200 ppm. The membranes are hollow fibers with diameters of about 0. the outside of the hollow fibers. 2. The fiber is a composite membrane consisting of an asymmetric polymer substrate and a polymer coating. with a high concentration of inerts. are concentrated on the shell side. The liquid flows through a control valve. recovered through the top and pass to the . 3 – 6 m. Heat exchange with cold product hydrogen fraction and with gas rejected to fuel cools the purge gas to a temperature of about 188  C (85 K). a dryer system is not required.1 – 0. The design of a single separator module (length. 56). serves as fuel for the primary reformer. This principle has been applied to separating hydrogen from other gases [814–817] (! Membranes: Gas-Separation Applications). i. Linde [777]. Trace concentrations of ammonia and water vapor in the gas stream pose no problem to the membrane. Production Processes the adsorbers next enters the cold box. diameter. Partial condensation liquefies methane and argon as well as some of the nitrogen and helium. Cryogenic hydrogen recovery units are supplied by firms such as Costain Engineering (formerly Petrocarbon Development) [707.5 mm. reducing its pressure. Reference [713] reports on the changes in operating conditions of an ammonia plant resulting from the operation of a cryogenic hydrogen recovery unit.. 3 Figure 56. 796. nitrogen. Hydrogen Recovery by Membrane Separation. The scrubbed purge gas is heated to 35  C and sent directly to the Prism separators. Gas separator module a) Nonpermeate gas outlet. Liquid ammonia from the ammonia plant may be used to provide additional refrigeration. especially at plant startup. The remaining gas. c) Hollow fiber. e) Coated carbon steel shell. Therefore. 0. g) Permeate gas outlet in a tubesheet at the other. and into a brazed aluminum (plate-fin or core-type) heat exchanger. b) Fiber bundle plug. a portion serves to regenerate the molecular sieves and then likewise flows to reformer fuel. and L’Air Liquide. 808–813]. methane.e. A bundle with many thousands of hollow fibers is sealed at one end and embedded Vol. among others. Hydrogen-rich permeate gas flows down the bore of the fiber and through the tubesheet and is delivered at the bottom of the separator.5 – 7 MPa). and argon. leaving a hydrogenrich gas. The entire bundle is encased in a vertical shell (Fig. The Monsanto Prism membrane separator system uses selective gas permeation through membranes to separate gases. The purge gas is water scrubbed at 135 – 145 bar. About 90 – 95 % of the hydrogen and 30 % of the nitrogen in the purge gas can be recovered. Hydrogen permeates through the wall of the fibers. 774–776. diameter.208 Ammonia. d) Separator (length. The warm hydrogen-rich gas flows back to the suction side of the second stage of the synthesis gas compressor (6. These are removed in a separator.2 m) resembles a shell and tube heat exchanger. f) Feed stream of mixed gases.

Of the recovered hydrogen. 786]. The ballast also is the binder for the pellets. is in the form of ballasted pellets. . The raw gas flows in axial direction in the high pressure spacer and the permeate is withdrawn in the low pressure spacer. this is used to supply the heat of desorption. Therefore.6. 824] Ammonia. such as LaNi5. . The second bank permeate hydrogen is recovered at 2. 231]: . an example is the Polysep Membrane System of UOP [783]. Therefore. then it may be possible to supplement the hydrogen recovery plant with one for recovering argon. A proprietary hydrogen separation process utilizing the reversible and selective adsorption capability of mixed metal hydrides has been proposed. ease of operation. The process. The hydride. Production Processes 209 and a process developed by Bergbau-Forschung [825] is offered by Costain. 785]. If potential markets for argon exist. The rate of permeation decreases across a bank of separators as the hydrogen partial pressure differential across the membrane approaches zero.1. In addition to the systems based on hollow fibers. p. Overall hydrogen recovery is 90 – 95 %. 781. Subsequently. 785. Cryogenic argon recovery from ammonia purge gas is discussed in [827–829]. Several separators operate in series. or Mg2Cu. Carbon-based adsorbents for pressure swing adsorption have also been investigated [823. with a purity of 99. The waste gas from hydrogen recovery plants is more highly enriched in argon than the purge gas. Reference [818] compares membrane and cryogenic separation units for a large ammonia plant. a second bank of separators with lower pressure on the tube side is used to increase the hydrogen recovery.5 – 2. 782.Vol. offers such a module under the name Serarex [784. preventing attrition. selection of the metal hydride must be based on the analysis of the gas to be treated. . is now marketed as Polybed PSA by UOP [783. Hydrogen Recovery Using Mixed Metal Hydrides. Membrane technology is also offered by other licensors. 3 next separator module. The system yields 99 mol % hydrogen product at a recovery efficiency of 90 – 93 % [826. for example. If required. membrane modules have been developed in which the membrane is in the form of a sheet wrapped around a perforated center tube using spacers to separate the layers. Argon Recovery from Ammonia Purge Gas. Hydrogen Recovery by Pressure Swing Adsorption. Inlet temperature: there are two opposed effects as increasing temperature enhances reaction rate but decreases the adiabatic equilibrium concentration. PSA technology is also offered by Linde and other companies. Influence of Pressure and other Variables of the Synthesis Loop The influences of individual parameters can be summarized as given in [771. No ammonia removal step is required upstream of the unit. Linde. For further literature on gas separation by membranes. Pressure swing adsorption on zeolite molecular sieves (PSA) (see Section 6. and low maintenance.999 %. The ballast material serves as a heat sink to store the heat of adsorption.3) may be also used for hydrogen recovery from purge gas [588]. 819–822]. but increases total ammonia production. the process also offers the possibility to supply pure hydrogen from the purge gas for other uses.8 MPa (25 – 28 bar) and returned to the first-stage suction of the syngas compressor. 823–825]. FeTi. see [779. Each type of metal hydride is susceptible to certain contaminants. 2. 6. No commercial installations are known to be in operation in ammonia production processes. The remaining nonpermeate gas stream normally flows to primary reformer fuel.3. The main advantages of the Prism separator system are simplicity. PSA units usually operate at adsorption pressures of 20 – 30 bar and achieve recovery rates higher than 82 % for hydrogen and 20 % for nitrogen. Pressure: increasing pressure will increase conversion due to higher reaction rate and more favorable ammonia equilibrium. 40 – 70 % leaves the first bank of separators at 7 MPa (70 bar) and is returned to the second-stage suction of the syngas compressor. originally developed by Union Carbide under the name HYSIV. Space velocity: increasing the space velocity normally lowers the outlet ammonia concentration. Typical argon recoveries are in excess of 90 %.

the temperature level for waste-heat recovery decreases and with lower temperature differences. Production Processes Inert level: increasing the inert level lowers the reaction rate for kinetic and thermodynamic reasons (Section 4. which translates into either a lower catalyst volume or a higher conversion.3). the feedstock) have to be weighed against investment. Hydrogen/nitrogen ratio: a true maximum reaction rate for a certain H/N ratio. Third. However. at current plant sizes of 1200 – 2000 t/d this constraint is no longer of importance.2): smaller catalyst particles give higher conversion because of lower diffusion restrictions (higher pore efficiency) The question of the best synthesis pressure is rather a difficult one and the answer is extremely dependent on optimization parameters such as feedstock price. Second. Analysis of the effects of various parameters on the energy consumption of the synthesis loop are also reported in [732. and site requirements. The front-end pressure determines the suction pressure of the synthesis gas machine. First. Thus the problem of choosing the best synthesis pressure is complex because not only does the entire energy balance have to be examined. and other studies came to higher values in the range 180 – 220 bar.3). the temperature of the ammonia separator determines the ammonia concentration at the converter inlet. These plants usually operate in the pressure range of 170 – 190 bar and it is a confirmation of the argumentation presented above that the different pressures are not reflected in the overall energy consumption of the complete ammonia plant. In a plant based on partial oxidation with an operating pressure of 80 bar. With the exception of some older processes which used extremely high pressures (Casale. The first of these plants. 3 and minimum possible temperature for the first bed. with a capacity of 600 t/d. for example. its energy level. . Of course. A lower temperature means lower ammonia concentration. at lower temperatures the maximum lies at lower H/N ratios (Section 4. for which a value of 155 bar is reported in [788. . the consequence of higher recycle rate is a lower ammonia concentration. and its impact on the energy balance of the complete ammonia plant. At constant equilibrium temperature for the effluent from the last bed (constant ammonia concentration) energy consumption of the loop was found to be almost independent of pressure in the range of 80 – 220 bar [790]. 150 bar by technical limitations of the centrifugal compressor. and especially the equilibrium temperature of the last bed [790]. the temperature attainable at a given site by air. Separator temperature: together with pressure and location of make-up gas addition. larger heat exchanger surface areas become necessary and the cross sections of piping and equipment have to be enlarged on account of the higher gas flow. and refrigeration are superimposed the result will be a minimum. In this case the difference to the equilibrium concentration and thus the reaction rate increases with the result that less catalyst is required. required return on investment. but also the mechanical design and the associated investment costs.1. 733]. 789]. the costs for energy (i. . such as grain size Vol. . were built in the mid-1960s and the maximum attainable synthesis pressure was restricted to ca. The result is strongly dependent on assumed boundary conditions.210 . Claude) a pressure of around 300 bar was common for the old multistream plants operated with reciprocating compressors. 2. and thus by any factors that affect it. this approach considers only the mechanical energy and ignores completely the recovered energy of reaction. Recycle rate: at constant pressure and production rate. Ammonia. such diagrams should be interpreted with care. For an actual project. Position of the maximum also depends on the space velocity values (Section 6. this type of plot is strongly influenced by the catalyst activity.or water cooling will affect the refrigeration duty.3. Catalyst particle size (Section 5. the type of front end can profoundly alter the result. .e. recycle. And fourth. The centrifugal compressor is one of the most important features of single-train ammonia plants. However. If plots of kilowatt hours versus synthesis pressure for make-up gas compression. as in a steam reforming plant with a suction pressure of only 25 bar.2). less than half as much energy is needed to compress the make-up gas to 180 bar.2). which needed a minimum gas flow (see also Section 6.. In principle it is possible to calculate the minimum amount of mechanical work needed in the synthesis loop.

18 98. b) Converter with one radial bed.23 3.20 0.79 47. Nielsen: An Investigation on Promoted Iron Catalysts for the Syntheses of Ammonia.26 18.09 0.00 0. 68 – 73.12 24. in G. 3 Ammonia.86 1.60 22.16 2.79 50.48 18. Honti. d) Heat exchanger.3. part 1.40 19. k) H2 recovery No.55 99.43 10. 1 separator.50 0.73 90. e) Water cooling. Example of a synthesis loop for 1500 t/d NH3 (Krupp – Uhde) a) Converter with two radial beds and internal heat exchange.72 72. D. Production Processes 211 Figure 57.38 18. The gas enters the converter (a) at 295  C and is subsequently heated in the internal heat exchanger to 390  C before it enters the first catalyst layer. G.67 8. 1 2 3 4 5 6 7 8 9 10 11 12 Flow rate. after which the gas leaves the converter with 469  C and passes a waste-heat boiler generating 125 bar steam.18 16. c) Waste-heat recovery.15 9.02 46.Vol.22 24.54 0.82 0.53 20.78 2.71 61.): The Nitrogen Industry.25 3.18 0. 2.01 inlet gas of the second vessel.  C 295 469 401 336 21 0 21 20 38 35 38 35 p.55 0. has a temperature of 401  C and the outlet enters a further waste-heat boiler generating 125 bar steam. References 1 A.20 73. Kopenhagen 1968.36 62. Hay.34 1.67 8.51 0.00 0. D. Budapest 1976.33 23. f) Heat exchanger. The outlet gas from the first layer then passes through the aforementioned heat exchanger and enters the second bed. pp. i) No.20 9.40 16.15 9.00 6.43 19.23 3. 2 separator.7. 2 I.20 Gas composition. t/h N2 H2 CH4 Ar NH3 23. Akademiai Kiado.07 2.31 1. Gjellerup. Honti (ed.51 4.20 0.93 61.99 54. MPa 18.89 5.21 0.25 18. Example of an Industrial Synthesis Loop Figure 57 is an example of modern ammonia synthesis loop (Krupp – Uhde) with two converter vessels and three indirectly cooled catalyst beds producing 1500 t/d NH3 at 188 bar.54 8. which accommodates the third catalyst bed. kmol/h 28344 25368 25368 24672 21613 28344 3060 3678 320 7667 374 8041 T.55 25.80 18.03 21.72 0.31 3.02 17. g) No.20 50.02 2.01 7.89 3.88 18.23 3. h) Refrigerated cooling. .50 0. j) NH3 recovery.37 4.30 0. mol % Production of NH3 liquid.88 0. The 51.43 20.

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2004. Further Reading T.1002/0471238961. Ammonia. p.): Corrosion handbook. Filippi. vol. Eggeman: Ammonia. Hoboken. F. 2. Kreysa. G. Sch€utze (eds. G. online: DOI: 10. Wageningen 2007. Dechema.0113131503262116.Vol. M. ed. E. E.. Production Processes 225 John Wiley & Sons. . Di Muzio.a01. NJ. Monteny. Wageningen Academic Publ. 2. Hartung: Ammonia emissions in agriculture. 2nd Casale Symposium for Customers and Licensees. 678–710. Kirk Othmer Encyclopedia of Chemical Technology. Wiley-VCH.pub3 (April 2010). 3 879 E.. 5th edition.-J. 2. Lugano 30 May – 2 June 2006. Rizzi. Weinheim 2007.